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Synthesis of 1,1-disubstituted alkyl vinyl sulfides via rhodium-catalyzed alkyne hydrothiolation : scope… Yang, Jun 2008

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SYNTHESIS OF 1,1-DISUBSTITUTED ALKYL VINYL SULFIDES VIA RHODIUM-CATALYZED ALKYNE HYDROTHIOLATION: SCOPE AND LIMITATIONS by JUN YANG B.Sc., Fudan University, 2006  A THESIS SUBMITTED iN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE  in  THE FACULTY OF GRADUATE STUDIES  (Chemistry)  THE UNIVERSITY OF BRITISH COLUMBIA (Vancouver) September 2008  © Jun Yang, 2008  Abstract 2 is a useful catalyst for alkyne hydrothiolation. Vinyl sulfides, the products ) 3 Tp*Rh(PPh of this reaction, are useful synthetic intermediates. The goal of this thesis project was to explore the scope and limitations of alkyne hydrothiolation with alkyl thiols catalyzed by . A variety of thiols and alkynes successfully undergo catalytic 2 ) 3 Tp*Rh(PPh hydrothiolation. In general, the branched isomer was formed in good-to-excellent yields and with high selectivity. Electron rich phenylacetylenes were more reactive than electron deficient ones, and provided higher yields. Aliphatic alkynes need longer reaction times than aromatic alkynes in order to reach complete conversion. A broad range of functional groups were well tolerated, including halides, amines, nitriles, amines, ethers, esters and silanes. Alkoxy groups with the ability to coordinate with rhodium slowed down the catalytic turnover and lowered the yields. Strongly coordinating groups, such as pyridine, precluded catalysis. Alkynes that are Michael acceptors react with reversed regioselectivity. Hydrothiolation using internal alkynes was successful, although the reaction times were longer and temperatures are higher than that needed for terminal alkynes. Overall, the work presented in this thesis provides a general method in construction of branched alkyl vinyl sulfides from alkynes.  11  Table of Contents  Abstract Table of Contents  lii  .  List of Tables  v  List of Figures  vi  List of Schemes  vii  List of Symbols and Abbreviations  vffl  Acknowledgements  Chapter 1  —  x  Introduction  1  1.1 Background  1  1.2 Hydrothiolation Reactions 1.2.1 Linear Isomers 1.2.1.1 Free Radical Hydrothiolation 1.2.1.2 Nucleophilic Hydrothiolation 1.2.1.3 Transition Metal-Catalyzed Hydrothiolation 1.2.2 Branched Isomer 1.2.2.1 Nucleophilic Hydrothiolation 1.2.2.2 Transition Metal-Catalyzed Hydrothiolation  3 3 4 4 6 8 8 9  1.3 Previous work of our group  13  1.4 Conclusions  16  2 Catalyzing Alkyne ) 3 Chapter 2 —Substrates Scope and Limitations of Tp*Rh(PPh Hydrothiolation  17  2.1 Introduction  17  2.2 Results and Discussion 2.2.1 Hydrothiolation of Benzylthiol and Aryl Alkynes 2.2.2 Hydrothiolation of Benzylthiol and Aliphatic Alkynes 2.2.3 Hydrothiolation of Phenylacetylene with Different Thiols 2.2.4 Hydrothiolation of Different Alkynes and n-Propanethiol 2.2.5 Hydrothiolation of Internal Alkynes and Other Cases  18 18 21 24 26 26  111  2.3 Experimental Procedures 2.3.1 General Methods 2.3.2 Materials and Methods 2.3.3 General experimental procedure for hydrothiolation  Chapter 3— Summary and Future Work  .28 28 28 29 69  4.1 Summary  69  4.2 Future Work  70  References  72  Appendices X-ray Crystallographic Data for Complex II  iv  77  List of Tables Table 2.1. Scope of Hydrothiolation of Aryl Alkynes with Benzylthiol Catalyzed by I. 19 Table 2.2. Scope of Hydrothiolation of Aliphatic Alkynes with Benzylthiol Catalyzed by I  22  Table 2.3. Scope of Hydrothiolation of Phenylacetylene with Different Thiols Catalyzed by I  25  Table 2.4. Scope of Hydrothiolation of Internal Alkynes Catalyzed by!  V  27  List of Figures Figure 1.1. Griseoviridin  .  1  2 ) 3 Figure 1.2. Tp*Rh(PPh  13  Figure 2.1. ORTEP diagram of complex II  21  Figure 3.1. Emtricitabine, Eletriptan, and Ertapenem  70  vi  List of Schemes Scheme 1.1.4 Scheme 1.2  7  Scheme 1.3  8  Scheme 1.4  9  Scheme 1.5  10  Scheme 1.6  11  Scheme 1.7  11  Scheme 1.8  12  Scheme 1.9  14  vii  List of Symbols and Abbreviations  MHz  angstroms (10’° meters) mu, micro broad calculated catalyst centimeters coupling constant degrees degrees Celcius deuterium 1 ,2-dichloroethane dihydrobisQ,yrazolyl)borate doublet electron impact equivalents ethyl frequency gamma gas chromatography-mass spectroscopy gram hertz high resolution mass spectroscopy hours hydrotris(pyrazolyl)borate iso isopropyl kappa kelvin kilocalorie liter low resolution mass spectroscopy mass/charge matrix-assisted laser desorptionlionization mega hertz  Me DCM tL mg  methyl dichioromethane microliter milligram  A br calcd cat. cm J o  °C d DCE Bp d El equiv. Et v GC-MS g Hz HRMS h Tp i i-Pr K  K kcal L LRMS m!z MALDI  viii  mL mmol mm M mol m n NMR ORTEP ppm Ph q rt SEM S t t  THF TEMPO 3 PMe PPh 3 UV Z E DBU Tp*  milliliter millimole minutes molar (mol L’) mole multiplet noimal nuclear magnetic resonance Oakridge Thermal Ellipsoid Plot parts per million phenyl pi quartet room temperature scanning electron microscopy singlet tertiary triplet tetrahydrofuran 2,2,6,6-tetramethylpiperidine-N-oxyl trimethyiphosphine triphenyiphosphine ultra violet zusammen entgegen 1 ,8-Diazabicyclo[5.4.O]undec-7-ene tris(3 ,5-dimethylpyrazolyl)borate tris(3 -phenyl,5-methylpyrazolyl)borate  ix  Acknowledgements Two years ago, it was my first time to set my first step on this beautiful land. Two years later, I finished my research and thesis under supervision of Dr. Jennifer A. Love. I would like to thank Dr. Love for her support, direction over the course of the project. Her enthusiasm, motivation and knowledge inspire me a lot in my graduate studies and researches. Her patience and advice help me stride over many difficulties. I would also thank all my group members, Paul Bichier, Heather Buckley, Alex Dauth, Lauren Fraser, Anthony Sabarre, Shiva Shoai, Duo Sun, Sara van Rooy and Tongen Wang for all of their help and support during the two years. I would like to give special thank to Lauren Fraser, Anthony Sabarre, and Shiva Shoai for their teaching, discussing and advising on my research, and to Paul Bichier, Alex Dauth, Duo Sun, and Tongen Wang for proofreading my thesis. Thanks also go to the NMR staff (Nick Burlinson, Zorana Danilovic, Maria Ezhova and Zhicheng Xia), the mass spectroscopy and elemental analysis staff (especially David Wang) and the stores staff. I really appreciate Brian Patrick for the X-ray crystal structures. I would like to acknowledge all my friends outside the lab, Xu Li, Ying Li, Yi Cao, Yuan Zhou, Ran Zhang and Xuefei Zhong. It is really a nice time to play cards and games with you guys. I also give my thanks to my parents, Guangming Yang and Mingxia Zhang, and my grandmother, Xiuzhu Yu. I will not be where I am today without their love and support. I also hope my grandfather Guangyang Zhang can get the news that I have finished my master’s study in the heaven. For my significant other, Xingzhi Yu, thank you very much for your support and positive motivation even when I was upset.  x  Chapter 1— Introduction  1.1 Background Sulfur is a very important element in nature. It is used in many industrial products such as rubber, detergents, fungicides, dyestuffs, agrichemicals, and medicines.’ Many natural products also contain C-S bonds. Griseoviridin, a broad spectrum streptogramin antibiotic, is only one of many examples. 2  OHOH  Figure 1.1. Griseoviridin  Vinyl sulfides are important synthetic intermediates and powerful building blocks 3 Cross coupling of vinyl halides and thiols is a for many natural and synthetic molecules. viable method to obtain vinyl sulfides. 4 However, alkyne hydrothiolation, the addition of a thiol to the it-bond of an acetylene, is a more atom-economical method to gain vinyl sulfide products, by converting all of the atoms in the starting materials into the products, thereby limiting waste production. Generally, in alkyne hydrothiolation of terminal alkynes, there are three potential products: branched, E-linear, and Z-linear isomers (eq 1.1). Free radical 5 and 6 hydrothiolation have been applied for making vinyl sulfides, but these nucleophilic  1  methodologies are generally limited to aryl thiols. Another significant disadvantage is that neither method can give branched products: free radical reactions only give the linear isomer without selectivity and nucleophilic reactions preferentially generate the Z-linear isomer.  RSH  +  1 R  +  R1c branched  RlSR E-linear  +  R1 (1.1) Z-Iinear  Transition metal catalyzed cross coupling reactions are widely used in the construction of carbon-heteroatom bonds. The use of amines, 7 alcohols 8 and phosphines 9 in cross coupling reactions with suitable substrates is well documented in the literature. However, because of the widespread prejudice that thiols are considered as catalyst poisons,’° the transition metal catalyzed addition of thiols to alkynes has not received as much attention. Moreover, the cases of synthesizing branched alkyl vinyl sulfides using transition metal are even scarce. Therefore, there is a great demand to find a general synthetic method towards the branched alkyl vinyl sulfides selectively.  2  1.2 Hydrothiolation Reactions As shown before, there are three major products in the hydrothiolation of alkynes. The branched isomer is formed from Markovnikov addition, whereas the E-linear and Z linear isomers are formed from anti-Markovnikov addition. Comparing the two linear products, the Z-linear isomer is kinetically favored while the E-linear isomer is thermodynamically more stable. In this section, the methods to form the linear and branched isomers will be discussed in detail.  1.2.1 Linear Isomers The first publication in this field was by H. Bader and co-workers in 1949.” In this paper, 1 -hexyne was treated with thio acetic acid and was heated for 10 mm to give 1hexenyl thioacetate in 53% yield (eq 1.2). The mechanism and stereoselectivity of this reaction were not mentioned. heat COSH 3 CH  +  9 H 4 n-C  3 SCOCH  9 H 4 n-C  (1.2) H  H 53%  Isomerization between E- and Z-linear adducts often accompanies the reaction (eq 1.3). Based on Truce and co-workers’ publication in 1972, the equilibrium could be achieved in 15 mm under dilute acidic conditions, while under basic condition it needed ’ The ratio of the E- and Z-linear isomers was approximately 3:1 6 hours or days.  R  1  conditions RSR  SR Z-Iinear  E-Iinear  3  (1.3)  .  1.2.1.1 Free Radical Hydrothiolation Free radical reactions were versatile in the synthesis of organic molecules, and free radical hydrothiolation has been under investigation since the 1960s. Usually this type of reaction was induced by either UV radiation or chemical initiators. ” However, the ratio 5 of the E- and Z-linear isomers was often hard to controL ’ Generally, the Z-linear isomer 5 was formed preferentially. In some cases, the ratio of the products depended on the ratio of thiol to alkyne. For example, in the free radical addition of benzenethiol to phenylacetylene, when the ratio of thiol to alkyne was 20:1, the Z-linear isomer was formed in 16% yield. When the ratio was changed to 1:1, the yield of the Z-linear isomer was 56%. In comparison, when the ratio was 1:20, the Z-linear isomer was formed in a 5 over 95% yield. In 1987, Oshima and co-workers reported the free radical hydrothiolation reaction B. The yields for aromatic thiol were good-to-excellent (70-91%), but for 3 catalyzed by Et aliphatic thiols, the yields were low even after prolonged reaction time. This problem can be solved by adding 4 equivalents of methanol. However, this reaction showed no stereoselectivity between the E and Z-linear isomers (see Scheme 1.1 )•5(1  B 3 Et  PhSH  +  21 H 10 n-C  21 H 10 n-C  SPh  =.(H  —  21 H 10 n-C H  SPh H  Scheme 1.1  1.2.1.2 Nucleophiic Hydrothiolation Nnucleophilic hydrothiolation favored the Z-linear product via trans-addition of a In the early stage of nucleophilic hydrothiolation, thiols were 6 thiol to a1kyne 4  deprotonated to the thiolate first and then reacted with acetylenes in ethanol to produce Z linear isomers in moderate to good yields  65 ( %)6a 87 ..  The reaction between p  toluenethiolate and acetylenes containing carbonyl groups, such as amide and acetyl, gave high degree of Z-adducts, but also had some E-adducts (about 10-20%). However the other activating groups such as p-tolysulfonyl, cyano, and p-nitrophenyl gave the Z adducts exclusively (eq 1.4).6c +  R—  R  __e  +  RSrl  Z-Iinear  E-Iinear  3 H C 2 O -[  92%  8%  NOC2 H  87%  13%  COC3 H  82%  18%  NEC--  100%  0%  100%  0%  100%  0%  (1.4)  In 2005, Oshima and co-workers reported stereoselective hydrothiolation catalyzed by cesium carbonate. Aryl alkynes and alkyl thiols were used in this reaction and the Z preferred. A free radical pathway was completely e linear isomer was found to be 6 inhibited by the radical inhibitor (TEMPO), so only nucleophilic hydrothiolation occurred. The electronic effect of the arylacetylenes had been examined: electron donating groups gave the Z-isomer exclusively but higher temperature was needed in order to get high yields; the electron withdrawing groups could help the reaction occur even at room temperature but without selectivity, and E-linear isomer was favored at high  5  reaction temperature. A limitation of this methodology was that aryl thiols were found to give poor yield even at high temperature.  1.2.1.3 Transition Metal-Catalyzed Hydrothiolation In 1976, Newton and co-workers discovered the first hydrothiolation reaction, catalyzed by molybdenum. Thiols were treated as both the electron and proton donor in the reaction. 12a The molybdenum catalyst facilitated the reaction between benzenethiol and dimethyl acetylenedicarboxylate in 25% yield with over 95% of the E-isomer (eq 1.5). SPh C 2 MeO  Me 2 CO  MoO [S C(1-  )] 2  C 2 MeO  16 PhSH  >95%  SPh CC02Me (1.5) 2 MeO <5%  The methodology for selectively synthesizing the E-linear isomer was greatly improved by Ogawa and co-workers in 1999. 12b They discovered that Wilkinson’s catalyst, CJRh(PPh , catalyzed the hydrothiolation of 1-octyne and benzene thiol in ) 3 good yield (62-97%). EtOH was found to be the best solvent and the reaction was completed after 20 hours at 20-40 °C with the E-linear isomer formed preferentially. Some mechanistic data had been obtained and the key step of the catalytic cycle was postulated to be migratory insertion of the alkyne into the Rh-H bond (see Scheme 1 .2).12l  6  RhClL PhSH  R  R  Rh(SPh)ClL  El  HRh(SPh)CIL  H  Scheme 1.2  The problem with this methodology was only benzene thiol was investigated as the thiol source and the author indicated that alkyl thiols did not work under the same conditions  12,c  Our research group has recently reported that Wilkinson’s catalyst did  catalyze hydrothiolation reaction using alkyl thiols with good regioselectivity of the E linear isomer, when the solvent was changed from ethanol to 1 ,2-dichloroethane (eq 1.6). 12d RSH R  +  = =  1 R  Aryl Alkyl  ClRh(PPh Solvent  = =  R S 1 R (1.6)  EtCH CH 2 CICH C I  In 2007, Yadav and co-workers reported InBr 3 to be an efficient catalyst in thiols. Aryl alkynes gave a mixture of linear products in e hydrothiolation using aryl 12  excellent yield with the E-linear isomer favored. However, when aliphatic alkynes were  7  used, the product was the corresponding thioacetal (see Scheme 1.3). All the reactions were completed in less than 30 minutes, but no mechanistic data were provided.  I  -  -  E:Z=7:3  (JSH PhS,,SPh 13 H 6 n-C  —  98 %  ( 1 H 6 n-C  Scheme 1.3  1.2.2 Branched Isomer Compared with the linear adducts, the branched product is much more difficult to access, and the examples of using alkyl thiols are uncommon. In Truce’s 1956 paper, some branched product was obtained together with the linear adducts using nucleophilic sodium p-toluenethiolate, but no selectivity was reported.oa  1.2.2.1 Nucleophific Hydrothiolation The few examples of hydrothiolation using aliphatic thiols that form the branched isomer regioselectively employ nucleophilic conditions. In 2005, Oshima and co-workers found terminal alkynes with a hydroxyl group can give the branched isomer in cesium carbonate mediated hydrothiolation (see Scheme 1.4).6e 3-butyn-l-ol gave 99% of branched product exclusively (n=2). Propargyl alcohol (n=l) and 4-pentyn-1-ol (n=3) gave a mixture of Z-linear and branched adducts in good and excellent yields respectively,  8  with the branched isomer favored. However, if n=4, the yield decreased significantly, but the stereoselectivity was still the same. No reasonable explanation was given in the paper. n1  H  25 H 12 SC  H  ‘‘—OH  H +  85 %  H  >==ç  15 C 2 H S 2  OH  74:26  H 25 H 12 SC OH H  n-2 -  OH n  99%  —  in +  12 H—SC 25 H (1.2eq) fl =  1  H  n=3  4  H  2 H 12 SC  H  +  H  SSOH H 2 Cl  89:11 H 36%  H  2 H 12 SC +  ).  H H0  84:16  >=-K 15 C 2 H S 2  H  HO—’  Scheme 1.4  1.2.2.2 Transition Metal-Catalyzed Hydrothiolation The first work of synthesizing branched vinyl sulfides was performed by Ogawa and co-workers in 1992.12c They discovered Pd(OAc) 2 catalyzed hydrothiolation and provided the branched isomer as the major adduct. However, only aryl thiols and a few alkynes were investigated, no alkyl thiol was employed, and the reactions needed high temperature and prolonged reaction times. A plausible reaction mechanism was also  9  provided. Migratory insertion of alkynes into Pd-S bond was considered as the key step of the reaction (see Scheme 1.5). 2 Pd(OAc)  +  2ArSH -2HOAc  L 2 Pd(SAr)  A” L 2 Pd(SAr) R  I  Pd(SAr)L  R  SAr  Scheme 1.5 Hydrothiolation of benzenethiol and conjugated terminal enynes with a terminal triple bond was achieved by Bãckvall and co-workers in 1994. In each case, the triple bond was found more reactive than the double bond, and the branched diene was formed in moderate yield (41-75%). 12f However, the reaction of internal enynes was not successful and only benzenethiol was used as a thiol source. Those products can be oxidized to the sulfoxide derivatives by oxone. Furthermore, those conjugated dienes could be further functionalized by Michael addition of a nucleophile, followed by [2,3] sigmatropic rearrangement to generate the allylic alcohol (see Scheme 1.6).  10  SPh cat. Pd(OAc) 2 +  HSPh  0 2 MeOH/H 64%  MeO 0 MeOH  60%  [  OH OMe  85%  Scheme 1.6 In 2007, Beletskaya and co-workers reported a novel approach for the preparation of iigands.l In this approach, Pd(OAc) one dimensional Pd nanoparticles with organic 2 2 dissolved in alkyne, reacted with thiol and generated nanostructured Pd species in 85% yield at room temperature (see Scheme 1.7). Both nm- and sum-scale Pd species could be prepared depending on different reaction conditions, but only nm-scale Pd nanoparticles had high efficiency and regioselectivity for the branched isomer in hydrothiolation reactions. 2 Pd(OAc)  +  R’  —  solution of Pd(OAc) in alkyne  RSH 8 Pd -HOAc  [Pd(SR)]  SR  Scheme 1.7  The hydrothiolation reaction occurred at 80-100 °C or under microwave heating. Cyclohexanethiol reacted with different terminal alkynes in good to excellent yields (7592%) with great regioselectivity for the branched isomer. Benzene thiol was less reactive but the regioselectivity was still good. A postulated reaction mechanism was also  ii  provided. Aikyne coordinated to palladium, migratory inserted into the Pd-S bond and trapped by thiol to generate the product (see Scheme 1.8). This is the second report about synthesizing the branched alkyl vinyl sulfide in hydrothiolation reaction. RS  ] 2 [Pd(SR) RSH  R/\ R’  Pd RS  R  Scheme 1.8  12  25 ( 2 Pd SR)  1.3 Previous work of our group The first example of synthesizing the branched alkyl vinyl sulfide via transition metal catalyzed hydrothiolation was reported by our group in Tp*  =  12h 2005  2 (I, ) 3 Tp*Rh(PPh  tris(3 ,5-dimethylpyrazolyl)-borate, Figure 1.2) was an efficient catalyst to give the  branched isomer predominantly in good to excellent yields arid selectivity. Ten examples using alkyl thiols were given. Aryl thiols were also found to generate the branched isomer preferentially, but the selectivity was lower. Because the products of the reactions using aryl thiols are readily available using other means, these reactions were not studied further. Instead, we chose to explore the use of alkyl thiols because the vinyl sulfide products are not readily available.  Tp*Rh(PPh Complex (I) 2 ) Figure 1.2. 3  A series of pyrazolylborate ligands, such as Tp* (tris(3,5.-dimethylpyrazolyl)borate), Bp*  (bis(3 ,5-dimethylpyrazolyl)borate),  phenyipyrazolyl)borate), and  TpMe  Tp  (trispyrazolylborate),  Tp”  (tris(3-  (tris(3 -phenyl,5-methylpyrazolyl)borate), were used  2 For the catalytic activity, Bp* <Tp to synthesize different kinds of rhodium complexes. ‘ <Tp’< TPPhMe  Tp*. Since the synthesis and purification of TpMe rhodium complex  Tp*Rh(PPh was chosen for scope and limitation investigations. 2 ) was more difficult, 3 A previous undergraduate student (Baldip Kang) had performed some preliminary studies) The reaction was believed to a mechanistic investigations using labeling 3  13  proceed via oxidative addition of the thiol, ligand exchange of triphenyiphosphine for the alkync, alkyne insertion into Rh-S bond, and reductive elimination to form the branched product and regenerate the catalyst (see Scheme 1.9). Further exploration of the reaction mechanism is underway.’ ’ 31  N  H  SR  H-  H  R’  i  3 ,PPh  N,,  3 PPh  3 PPh  3 PPh HEER H’B 3 PPh  N  ==-  I  3 PPh  Scheme 1.9  Tp*Rh(PPh was found to decompose in 2 ) Another important observation is that 3 THF and DCE if left for prolonged time, producing a complex via orthometalation of one of the phosphine ligands (eq 1.7).’ Although it formed a strained four-membered ring, this process was determined to be irreversible. This would be detrimental to a catalytic  14  reaction, as it would remove the active catalyst. The cyclometalation could be avoided once some nonpolar solvents were used, such as benzene and toluene. For hydrothiolation, slightly polar solvents are needed. Thus, a 1:1 ratio of toluene and DCE was found to be optimal for hydrothiolation and would preclude catalyst decomposition even if prolonged reaction times were needed.  ui  -N,  3 PPh  N’  PPh  DCE  (1.7) h  (73%)  2 was demonstrated to not only work in alkyne hydrothiolation, but ) 3 Tp*Rh(PPh also catalyze alkyne hydrophosphinylation (eq 1.8).’ Compared with hydrothiolation, in which the branched isomer was formed predominantly, it was expected to produce the same isomer for hydrophosphinylation. Upon investigation of this hypothesis, it was 2 did catalyze alkyne hydrophosphinylation, although not as well ) 3 found that Tp*Rh(PPh as Wilkinson’s catalyst. In addition, the product was not the branched isomer, but the E ) reacted 3 linear adducts. It was postulated that both Wilkinson’s catalyst and Tp*Rh(PPh with Ph P(O)H to generate the active catalytic species and that this process was more 2 efficient with Wilkinson’s catalyst.  2 P(O)Ph P(O)H 2 Ph  +  R  11  +  branched  15  R°12 E-Iinear  +  R 2 (1.8) P(O)Ph Z-Iinear  1.4 Summary Vinyl sulfides are important synthetic intermediates in total synthesis and useful building blocks for many highly functionalized molecules. Transition metal catalyzed alkyne hydrothiolation is an efficient method to produce vinyl sulfides. Methods of forming the E- and Z- linear adducts have been investigated widely. However, most Tp*Rh(PPh is a 2 ) methods of making branched isomer are limited to aryl thiols. 3 promising catalyst for alkyne hydrothiolation reaction, giving branched alkyl vinyl sulfides predominantly. Given that this process provides a useful strategy for the formation of branched alkyl vinyl sulfides, we wanted to explore the substrate scope and limitations of this catalyst. As such, the goals of this research project were to evaluate functional group tolerance, as well as steric and electronic effects in alkyne . 2 ) 3 hydrothiolation catalyzed by Tp*Rh(PPh  16  Chapter 2 —Substrate Scope and Limitations of 2 Catalyzing Alkyne Hydrotbiolation ) 3 Tp*Rh(PPh  2.1 Introduction Ailcyne hydrothiolation, as discussed in chapter 1, is the addition of an S-H bond across an alkynyl it-bond and is a very efficient method for the synthesis of vinyl sulfides (eq 2.1). Although aryl vinyl sulfides can be made by radical, 5 nucleophilic, 6 and metal2 reactions, a general synthetic method of the branched alkyl vinyl sulfides is catalyzed’ still not well developed.  RSH  SR +  +  1 R  R,SR  +  R  (2.1) SR  1 R branched (a) E-Iinear (b)  Z-Hnear (c)  Tp*Rh(PPh (I, Figure 1.2)1211 and TpPle 2 ) Our group has recently reported that 3 2 are excellent catalysts for alkyne hydrothiolation using alkyl thiols to generate ) 3 Rh(PPh branched alkyl vinyl sulfides.’ ” In our early work, we reported ten examples of alkyne 2 hydrothiolation. We wanted to explore the scope in greater detail. Since the synthesis and purification of the TpPl1Me rhodium complex was difficult and time consuming, 2 was chosen for the scope and limitations investigation. ) 3 Tp*Rh(PPh  17  2.2  Resi1ts and Discussion A broad range of thiols and alkynes were selected for investigation. The reactions  are classified into five parts: (1) hydrothiolation of benzylthiol and aryl alkynes, (2) hydrothiolation  of benzylthiol  and  aliphatic  alkynes,  (3)  hydrothiolation  of  phenylacetylene with different thiols, (4) hydrothiolation of different alkynes and n propanethiol, and (5) hydrothiolation of internal alkynes and other cases. The hydrothiolation using n-propanethiol was done by another group member (Anthony Sabarre), and some reactions from this previous work will be cited. In a typical experiment, PhCH 3 (2 mL), 1 ,2-dichloroethane (DCE, 2 mL) and 2 (280 mg, 0.30 mmol, 3 mol ) 3 Tp*Rh(PPh  %) were combined in a 20 mL vial equipped  with a magnetic stir bar and a screw cap. Thiol (11 mmol, 1.1 equiv relative to alkyne) and alkyne (10 mmol) were then added and the solution was stirred at room temperature for 2 hours. In some cases longer reaction times and higher temperatures were needed; these conditions will be noted in the text and in the experimental section.  2.2.1 Hydrothiolation of Benzylthiol and Aryl Alkynes We first examined the electronic effect ofpara-substituted phenylacetylenes (Table 2.1, entries 1-6). The electronic modifications at the para- position did not influence the reaction regioselectivity, but had a significant effect on the reaction efficiency and yield. The branched isomers were the only product of these reactions. Alkynes with electrondonating groups (entries 1-4) gave excellent yields, but those with electron-withdrawing groups (entries 5 and 6) gave lower yields. The methoxy group at meta- position (entry 7) also gave a very good isolated yield, however the yield of the reaction of ortho methoxyphenylacetylene (entry 8) was much lower even after 24 hours. There are two  18  potential explanations for these results: the methoxy group at the ortho- position could be too bulky and/or the oxygen of the ether could coordinate to rhodium. Both scenaiios would lead to slower catalysis. We chose a more sterically demanding ortho methyiphenylacetylene (entry 9) for further investigation and found that the yield was still good. Since the methyl group cannot coordinate to rhodium easily, we concluded that the coordination of oxygen to rhodium was the reason for the low reaction efficiencyand yield indicated in entry 8. An alkyne with a strongly coordinating group, 2pyridylacetylene (entry 10), showed no reactivity at all.  Table 2.1. Scope of Hydrothiolation of Aryl Alkynes with Beiizylthiol Catalyzed by I. 3 mol% I  8 entry  SH  +  Ar—  2h,rt Ar  product, yield”  1  N—-[2 Me  Ia, 90%  2c  CO3 H  2a, 93%  S  (1:1) 3 DCE:PhCH  —  Ph  8 entry  Ph  Ar Ar C—(J—— 3 F  7  product, yield” 6a, 40%  7a, 83% 3 OCH  3  4C  C—’-— 3 H  3a, 91%  8  8a, 55%  H—K--—  4a, 90%  9  9a, 85%  Br—(D-—  5a, 67%  10  0%  a  Reaction conditions: 10 mmol alkyne, 11 mmol thiol, 4 mL of 1:1 DCE:PhCH , and 0.3 3 mmol (3 mol %) catalyst, at room temperature for 2 h, unless otherwise noted. b Isolated yields. C Ref 12h, d An additional 5-10% of an unidentified byproduct was observed. Reaction time 24 h.  19  In order to get more information about why 2yridylacetylene did not react, we 2 (93 mg, 0.1 nirnol) was dissolved in d ) 3 conducted the following reaction: T*Rh(PPh 8 =  toluene (1 mL), and 2-pyridylacetylene (0.1 mL, 1.0 mmol) was then added. After 30 minutes, the color of the solution changed from orange to black, and the ‘P N 2 (642.92, d, J ) 3 specum showed that the PPh 3 sigual Tp*Rh(PPh vanished and both a new doublet (6 45.90,  Jp  appeared. A rhodium hydride species (6 -14.68,  =  =  175.6 Hz) had  124.7 Hz) and new singlet (6 -4.56)  JRh-H  =  20.5  HZ,JPH  =  17.6 Hz) was also  detected in the ‘H NMR spectrum. The solution was transferred to a 5 mL vial, layered with 2 mL of hexanes; crystals suitable for X-ray diffraction formed after 2 days at room temperature. The ORTEP diagram (Figure 2.1) indicated that the terminal C-H bond of alkyne was activated and a rhodium hydridoacetylide (complex II) was generated. The bond lengths and angles of complex II was very similar to other reported rhodium 4 hydridoacetylieds.’ We have previously reported that such a C-H activation process irreversible and that the resulting complex has no reactivity in alkyne hydrothiolation reactions. 14 In addition, we have found that hydrothiolation proceeds by S-H activation, followed by ailcyne migratory insertion. 13a In other words, S-H activation must be faster than C-H activation. The same phenomenon was also observed in the catalytic reaction. Thus, we thought since that binding of pyridine suppresses thiol coordination. As a result, 2pyridylacetylene is in close proximity to the metal center, which facilitates C-H activation, thereby suppressing catalysis.  20  C15 C13 C14  cii  C12  C39  H2 C40 C5  do  C34  Ni Hf  C33  N3  Rh1  I  j___Y  C16  C30 Cl 9 C20 C24  Figure 2.1. ORTEP diagram of complex II. Thermal ellipsoids are drawn at the 50% probability level. Hydrogen atoms, except for the B-H hydrogen and the phenyl groups of , are excluded for clarity. Selected bond lengths 3 PPh Rh-C(34)  =  1.9627(17), Rh-H  =  (A), angles (deg): Rh-P 2.2732(5),  1.46(2), C(34)-C(35)  88.72(5), C(34)-Rh(l)-H(1) = 83.8(9), P(l)-Rh(1)-H(1)  =  =  =  1.212(2), C(34)-Rh(l)-P(l)  =  88.1(8).  2.2.2 Hydrothiolation of Benzylthiol and Aliphatic Alkynes  Hydrothiolation of aliphatic alkynes was studied next. Compared to aromatic alkynes, the reactions of aliphatic alkynes need longer time to complete, but the yields and selectivities were still very good. 3-Phenyl-1-propyne (Table 2.2, entry 1), 5hexynenitrile (entry 2), 5-chloro- 1 -pentyne (entry 3), and 1 -octyne (entry 4) reacted with benzyl thiol in good-to-excellent yields. The lower yield of phenyl propargyl ether (entry  21  5) could also be attributed to the coordination of oxygen to rhodium. In addition, the  product of entry 6 and its oxidized derivatives may be suitable for Diels-Alder reactions.  Table 2.2. Scope of Hydrothiolation of Aliphatic Alkynes with Benzylthiol Catalyzed by I. 3 mol% I PhSH  (1:1) 3 DCE:PhCH  R  +  R  entrya  R  I  time (h)  product, yield”  entrya  24  lOa,85%  6c  48  11 a, 88%  2  NC-  3  Cl_\  24  12a, 90%  4  13 H 6 n-C j--  16  13a, 92%  5  PhO\  24  14a,  °“  R  time (h)  product, yield”  10  15a,81%  7C  t-Bu--  24  16a, 63%  8  TMS--  2  17a:17b:17c = 6:3:2, 88%  9  EtOC-[  2 =  18b:18c 2:1, 68%  a  Reaction conditions: 10 mmol alkyne, llmniol thiol, 4 mL of 1:1 DCE:PhCH , and 0.3 3 mmol (3 mol %) catalyst, it b Isolated yields. C Ref 1 2h.  The products of the alkynes containing propargylic protons (entries 1-4) can isomerize under acidic conditions. For example, when benzyl(1-benzylvinyl)sulfane (lOa) was let to stand in chloroform overnight, 13% of Z- and 25% of E- internal vinyl sulfide were found (eq  2.2).12h1  This phenomenon could be avoided if less acidic solvents were  used for chromatography and NMR spectroscopic studies (eq 2.3).  22  SPh  3 CHCI  SPh  Ph  Ph  lOa  S’Ph +  62%lOa  S  Ph  Ph  +  Ph  I  13%lOb  25%lOc  no isomerization  (2.3)  (2.2) Ph  Benzene  I Oa  The effect of sterics was also investigated. The reaction of 3 ,3-dimethyl- 1 -butyne (entry 7) took 24 hours to go to completion and formed the branched isomer in moderate yield, indicating that sterically bulky groups can somewhat slow catalysis. If trimethylsilyl acetylene (entry 9) was used, the reaction was complete in 2 hours, but the regioselectivity was lowered, with 40% of the the linear isomers being formed. It is not clear why the selectivity was lowered, but could be due to the beta-silicon effect. Trimethylsilyl groups are useful functional groups that can be easily deprotected or further functionalized in Hiyama’ 6 cross-coupling. The hydrothiolation of ethyl propiolate gave a mixture of E- and Z-linear isomers in a 2:1 17 ratio. No branched product was formed in this case. This result was likely due to the strongly electron withdrawing ester group, which activates the beta-position of the alkene toward nucleophilic attack. The use of DBU generates a 1:2 ratio of E- and Z-linear isomers after 2 h at room 2 is not simply due to competing ) 3 temperature. Therefore, the result using Tp*Rh(PPh Michael addition. Several competing mechanisms are possible.  23  2.2.3 Hydrothiolation of Phenylacetylene with Different Thiols Given that a variety of alkynes were found to be effective in hydrothiolation, we next examined the substrate scope of thiols that participate in this reaction. Besides benzyl thiol (Table 2.3, entry 1), a variety of alkyl thiols reacted with phenylacetylene in good yields, including both unhindered (entry 2) and sterically bulky (entry 3) groups. Many functional groups were well tolerated, such as heteroaromatic rings (entry 4), ethers (entry 5), esters (entry 6) and amines (entry 7). However, the reaction of thiols with a carboxylic acid (entry 8) or allyl group (entry 9) failed. In the latter case, since the n-propanethiol (entry 2) reacted with phenylacetylene successfully, we thought the double bond should play an important role in this process. This was disappointing, because if the allyl mercaptan (entry 9) reacted successfully, the product could undergo several transformations, such as thio-Cope’ 8 and Mislow-Evans’ 9 rearrangements (upon oxidation to the sulfoxide).  24  Table 2.3. Scope of Hydrothiolation of Phenylacetylene with Different Thiols Catalyzed by I. 3 mol% I RSH  +  Ph  1c  L  Ph”  2 h, rt  entrya  SR  3 (1:1) DCE:PhCH —  R  product, yieId’  Ph  Ia, 90%  entrya  R  product, yield”  0 23a, 80%  6 BuO  2’  19a, 74% 7e  3C  20a, 78%  4  21a, 75%  5  Ph0-’.  N 2 Me  24a, 65%  C/ 2 H0  0%  ge  22a, 70%  0%  a  Reaction conditions: 10 mmol alkyne, 11 mmol thiol, 4 mL of 1:1 DCE:PhCH , and 3 0.3 mmol (3 mol %) catalyst, at rt for 2 h, unless otherwise noted. b Isolated yields. C Ref 12h. d Ref 3f e Reaction time: 24 h.  Further insight was obtained from the following stoichiometric reaction. A d 8 2 (93 mg, 0.1 mmol) was placed in a NMR tube, ) 3 toluene (1 mL) solution of Tp*Rh(PPh  and allyl mercaptan (0.08 mL, 1.0 mmol) was added by syringe. After 30 minutes, the 31 P 2 (6 42.92, d, J ) 3 NMR spectrum showed that the PPh 3 signal Tp*Rh(PPh  =  175.6 Hz)  disappeared and a new singlet (6 -4.56) appeared, which indicated that both of the PPh 3 ligands had dissociated. However, no rhodium hydride species were found in the ‘H NMR spectrum, although the methylene resonance of thiol changed from a doublet of  25  doublets (ö 3.16, J  7.0 Hz, J= 7.0 Hz) to a doublet (ö 2.78, J= 6.9 Hz). This data could  indicate that diallyl sulfide formed in this process, but no further information can be provided from GC-MS analysis. Nonetheless, the data showed that the allyl mereaptan , but not in the same way that other thiols react. 2 ) 3 did react with Tp*Rh(PPh  2.2.4 Hydrothiolation of Different Alkynes and n-Propanethiol The catalytic hydrothiolation of n-propanethiol and various alkynes was investigated 3 Similar to the reactions of benzyl thiol, all reactions proceeded by Anthony Sabarre. with high selectivity of branched products. Likewise, the reactions of para-substituted phenylacetylenes with benzyl thiol followed the same trends. All the hydrothiolation products proved to be suitable for Kumada-type cross-coupling to generate 1,1d, 3 oleflns disubstituted 20  2.2.5 Hydrothiolation of Internal Alkynes and Other Cases The catalytic hydrothiolation reactions of internal alkynes were found to be much more difficult to achieve than with terminal alkynes. Longer reaction times were always needed and sometimes high temperature was necessary (Table 2.4). While the reaction between cyclopentyithiol and diphenylacetylene proceeded in excellent yield providing a single isomer (entry 1), only a trace of the desired product can be found in the reaction using benzyl thiol (entry 2). Cyclotrimerization ’ occurred when 3-hexyne was used, and 2 the yield of expected product was only 32 % (entry 3). The reaction of 1-phenyl-1propyne gave a moderate yield and favored the less-hindered isomer as product (entry 4).  26  Table 2.4. Scope of Hydrothiolation of Internal Alkynes Catalyzed by I 3 mol% I RSH  entrya  =R 1 R 2  +  alkyne  R  Ph  IC  —  3 (1:1) DCE:PhCH  temperature, time  Ph  product  S  80 °C, 24 h  25a, 94%  Ph 2  Ph  3  Ph  4C  Ph)  Ph  :ii  Ph  rt, 24 h  Et  El  Et  rt, 24 h  Ph  El  Me  50°C,4h  yield”  product  Ph trace  26a,  Ph  %d 32  S—\ 27a:27b= Ph :3.5,7Oiod 1  +  Ph’  Reaction conditions: 10 mmol alkyne, 11 mrnol thiol, 4 mL of 1:1 DCE:PhCH , and 3 b C d 0.3 mmol (3 mol %) catalyst. Isolated yields. Ref 12h Yield based on 1H NMR analysis.  Finally we achieved a successful hydrothiolation of 1,6-hexanedithiol and 2.2 equivalents of 4-methoxyphenylacetylene and obtained 80% of desired product after 24 hours at room temperature (eq 2.4). None of the mono-addition product was detected, although this species is likely an intermediate in the formation of 28a. 2 ) 3 3 mol% Tp*Rh(PPh +  CO—€J?—-_ 3 H  (2.4)  DCE:Tolene(1:1) 24h, rt, 80% 28a  27  2.3 Experimental Procedures  2.4.1 General Methods Manipulation of organometallic compounds was performed in a nitrogen-filled Vacuum Atmospheres drybox (02  <  2 ppm). NMR spectra were recorded on Bruker  Avance 300 or Bruker Avance 400 spectrometers. ‘H, ‘ P chemical shifts are C and 31 3 reported in parts per million and referenced to residual solvent. Coupling constant values were extracted assuming first-order coupling. The multiplicities are abbreviated as follows: s  =  singlet, d  =  doublet, t  triplet, quin  =  quintet, m  multiplet). 31 P{1H} NMR  spectra were referenced to an external 85% 4 P0 standard, and ‘ 3 H F NMR spectra were 9 referenced to CFC1 3 standard. All spectra were obtained at 25 °C. Elemental analyses were performed using a Carlo Erba Elemental Analyzer EA 1108. Mass spectra were recorded on a Kratos MS-50 mass spectrometer.  2.4.2 Materials and Methods. Hexanes (boiling range 68.3-69.6 °C), 2 C1 Et CH , 0, THF, benzene, PhCH 2 3 and DCE (1 ,2-dichloroethane) were dried by passage through solvent purification columns. 22 3 was distilled from P CDC1 5 and was degassed prior to use. C 0 2 D was purified by 6 vacuum transfer from Nalbenzophenone. All organic reagents were obtained from commercial sources and used as received. Wilkinson Catalyst was purchased from Strem 2 (1)23 was prepared as } 3 Chemicals and was used without further purification. Tp*Rh(PPh previously reported. 12j  28  2.4.3 General experimental procedure for hydrothiolation. 2 (280 mg, 0.30 mmol, 3 mol %), PhCH ) 3 Tp*Rh(PPh 3 (2 mL), DCE (2 mL) were combined in the glove box in a 20 mL vial equipped with a magnetic stir bar and a screw cap. Thiol (11 mmol) and alkyne (10 mmol) were added sequentially. The vial was removed from the glove box. The vial was then wrapped in aluminum foil and the solution was stirred at the indicated temperature and monitored by TLC. After the reaction was completed, the resulting mixture was filtered through silica gel, washed by hexanes, concentrated under vacuum. Flash chromatography (Si02, hexanes or a mixture of hexanes: EtOAc as eluent) provided the product. Note: The reactions proceed very slowly in the absence of the catalyst, indicating that background reactions are minimal. The addition of a non-nucleophilic base (2,2-lutidine) does not impede or improve the h1 12 reaction.  Analytical data for 2a, 4a, 13a, 15a, 16a, 19a, 20a, 25a, and 27a,b were  previously reported. 12h  29  3 +  XSH  Me2N-Q--  ;:.;:2  2h,rt,90%  Benzyl(1-(4-N,N-dimethyphenylvinyl)sulfane  (la):  QQ Ia  Yellow oil,  90%  yield.  Column chromatography conditions: 20:1 hexanes:EtOAc and 3 % Et N. ‘H NMR 3 , 300 MHz): ö 7.47 (d, 2H, J= 8.7 Hz), 7.31 3 (CDC1  —  7.23 (m, 5H), 6.71 (d, 2H, J= 9.1  Hz), 5.36 (s, 1H), 5.08 (s, 1H), 3.90 (s, 2H), 2.99 (s, 6H), 1.55 (H 0). 1 2 C{ 3 ‘ H } NMR , 100 MHz): 3 149.3, 145.7, 138.5, 129.9, 129.4, 129.1, 128.2, 128.0, 113.0, 3 (CDCI 110.1, 41.5, 38.2. HRMS (El) mlz calcd for SN: C 1 H 7 269.1238; found: 269.1236. Anal. 9 calcd for SN: C 1 H 7 C, 75.79; H, 7.11; N, 5.20; found: C, 75.72; H, 7.16; N, 5.53. 9  30  ‘H NMR (CDC1 , 300 MHz) 3  s-r N’- Ia 2 Me  9.5  9.0  8.5  80  7.5  7.0  C NMR (CDC1 3 ‘ , 100 3  6.5  6.0  5.5 5.0 45 Chen,il Shift (ppm)  MHz)  45  3:5  30  25  2.0  1.5  1.0  0.5  r0 N Ia 2 Me  I..l]  102  184  176  168  160  152  144  136  128  120  112  1ó4 9 8 Chomical Shift (ppm)  31  8072645646403224  l6  3rn%Tp*Rh(pph3)2 OSH  +  2h,rt,91%  Benzyl(1-p-tolylvinyl)sulfane  (3a):  Yellow  3a  oil,  yield.  91%  Column  chromatography conditions: 20:1 hexanes:EtOAc. ‘H NIvIR (CDC1 , 300 MHz): 3 ö 7.47 (d, 2H, J = 8.2 Hz), 7.34  —  7.27 (m, 5H), 7.20 (d, 2H, J = 7.8 Hz), 5.47 (s, 1H),  5.21 (s, 1H), 3.93 (s, 2H), 2.40 (s, 3H). ‘ C{’H} NMR (CDC1 3 , 100 MHz): ö 145.9, 3 139.4, 138.1, 137.6, 130.1, 130.0, 129.5, 128.2, 128.1, 112.2, 38.2, 22.2. HRMS (El) mlz calcd for S H: 6 C, , 240.0967; found: 240.0973. Anal. calcd for 7 C, S 2 H N: C, 79.95; H, 6.71; found: C, 79.73; H, 6.62.  32  V  H NMR (CDC1 1 , 300 MHz) 3  sAN  L3a  CheniI Shift (ppn)  c NMR (CDC1 3 ‘ , 100 MHz) 3  SN  CherniI Shift (ppn)  33  3rn01%Tp*Rh(pph3)2 +  Br—(— Br  2h,rt,67%  5a  Benzyl(1-.(4-bromophenyl)vinyl)sulfane (5a): Pale yellow oil, 67% yield. Column chromatography conditions: 20:1 hexanes:EtOAc. ‘H NMR (CDC1 , 300 MHz): 3 8 7.48 (d, 2H, J = 8.7 Hz), 7.41 (d, 2H, J = 8.7 Hz), 7.32  —  7.22 (m, 5H), 5.44 (s, 1H),  5.23 (s, 1H), 3.88 (s, 2H), 1.54 (H 0). ‘ 2 C{’H} NMR (CDC1 3 , 75 MHz): 6 144.0, 138.5, 3 136.9, 131.7, 129.0 (two peaks overlaping), 128.7, 127.4, 122.6, 112.9, 37.3. HRMS (El) C 1 H 7 S 5 303.9921; found: 303.9919. Anal. calcd for Br: 3 9 mlz calcd for Br: H 5 C, 7 S 3 9 , C, 59.02; H, 4.29; found: C, 58.64; H, 4.40.  34  ‘H NMR (CDC1 , 300 MHz) 3  95  l3  90  85  80  7  70  65  sThI  60  55 50 45 Choi 0501 (pp,)  40  35  3.0  Br’  5a  1.5  1.0  25  20  0.5  NMR (CDC1 , 75 MHz) 3  rT0 Br’-  1flflMMIR!$L1IIIUflhIIH1 1à2  14  5a  ‘‘‘  1761681601521441361281011210496 88 Chn4I 0148 (ppo)  35  80  72&1  56  48  40  32  24  16  8  ftfSH  +  C_4J__ 3 F  DC; Ph 2h,rt,40%  C 3 F  6a  Benzyl(1-(4-(trifluoromethyl)phenyl)vinyl)sulfane (6 a): Yellow oil, 40% yield. Column chromatography conditions: 20:1 hexanes:EtOAc. ‘H NMR (CDC1 , 300 MHz): 3 6 7.65 —7.58 (m, 4H), 7.33 —7.23 (m, 5H), 5.52 (s, 1H), 5.31 (s, 1H), 3.90 (s, 2H), 1.53 F NMR (CDC1 9 , 282 MHz): 6 -63.1 (d, J 3 0). ‘ 2 (H  4.2 Hz). ‘ C{’H} NME. (CDC1 3 , 100 3  MHz): 6 143.8, 143.0, 136.6, 130.4 (q, J= 33.0 Hz), 128.8, 128.5, 127. 5, 127.3, 125.4 (q, J  =  3.8 Hz), 124.1 (q, J  =  272.2 Hz), 113.9, 37.3. HRMS (El) m!z calcd for  SF C 1 H : 3 6 294.0690; found: 294.0702. Anal, calcd for SF 3 C 1 H : 3 6 C, 65.29; H, 4.45; 3 found: C, 64.94; H, 4.36.  36  s---  H NMR (CDC1 1 , 300 MHz) 3  C 6a 3 F  95  90  85  80  75  c APT NMR (CDC1 3 ‘ , 3  70  65  60  50 50 45 Chon*I Shift (pprmm)  40  35  30  25  20  15  10  05  100 MHz) C- 6a 3 F  -ri_.r r  s.-.-  :rrr.  V  V  t.ui  .  V  —rr-r  ri,  .,  ’’’’ 1 jUL  LJ.Lr.it  192184176166  160152  144  136128  120112  164 86 8580 Chen4I Shift (ppm)  37  72  6456  4540  3224  16  8  3rno(%Tp*Rh(pph3)2 +  CO 3 H  2 h, rt, 83%  3 OCH  7a  Beuzyl(1-(3-methoxyphenyl)vinyl)sulfane (7a): Yellow oil, 83% yield. Colunm chromatography conditions: 20:1 hexanes:EtOAc. ‘H •NMR (CDC1 , 300 MHz): 3 ö 7.32  —  6.90 (m, 9H), 5.50 (s, 1H), 5.25 (s, 1H), 3.93 (s, 2H), 3.84 (s, 3H). ‘ C{’H} 3  NMR (CDC1 , 75 MHz): ö 159.8, 145.1, 141.0, 137.2, 129.6, 129.1, 128.7, 127.3, 119.9, 3 114.4, 112.9, 112.2, 55.5, 37.4. HRMS (El) mlz calcd for 6 H, 1 C S 6 256.0922; found: 0: 256.0921. Anal. calcd for H S0: C 1 6 C, 74.96; H, 6.27; found: C, 74.59; H, 6.27.  38  , 300 MHz) 3 ‘H NMR (CDC1  a  3 OCH  ““  ““  ChrnicaI Shift (ppn)  , 75 MHz) 3 C NMR (CDC1 3 ‘  3 7a OCH  I  1ir 192  194  176  168  160  152  144  -jJunILMJ ii 136  128  120  112  104 96 88 Chornii Shift (ppn)  39  80  77  64  56  thJK; &i 48  40  32  tJi 24  ttt 16  8  :::;3)2 +  3 OCH  24 h,  ‘  JL1IDJ OCH 3 Ba  Benzyl(1-(2-methoxyphenyl)vinyl)sulfane (8a): Pale yellow oil, 55% yield.  Column chromatography conditions: 20:1 hexanes:EtOAc. ‘H NMR (CDC1 , 400 MHz): 3 ö 7.31  —  7.21 (m, 7H), 6.96  —  6.90 (m, 2H), 5.37 (s, 1H), 5.34 (s, 1H), 3.90 (s, 2H), 3.84  (s, 3H). C{ , 100 MHz): ö 157.1, 142.7, 138.1, 131.5, 130.4, 129.9, 3 13 H 1 } NMR (CDC1 129.4, 128.0, 121.6, 121.5, 114.4, 112.29, 56.8, 38.2. HRMS (El) mlz calcd for S0: C 1 H 6 256.0922; found: 256.0923. Anal. calcd for H SO: C 1 6 C, 74.96; H, 6.27; found: C, 74.79; H, 6.35.  40  ‘H NMR (CDC1 , 400 MHz) 3  SQ  I  I 9.5  9.5  8.5  8.0  7.8  7.0  6:5  6.0  5.5 5,0 4.5 Chnil Shift (ppm)  4.0  3.5  3.0  2:5  2.0  1.5  1.0  0.5  C NMR (CDC1 3 ‘ , 100 MHz) 3  ç-c OCH 3 8a  b.88  :‘  192  084  076  168  160  152  144  ‘  136  128  120  112  -  ,:.‘,.,o’o.,t’T’-.  104 96 88 ChemftI Shift (pp,n)  41  60  1  I L -9,b._  ,-,,,.,-  72  64  56  48  40  32  24  16  8  JSH  +  Q—  Benzyl(1-o-tolylvinyl)sulfane  3;.:3)2  2h,rt,85%  (9a):  Pale  yellow  9a  oil,  85%  yield.  Column  chromatography conditions: 20:1 hexanes:EtOAc. ‘H NMR (CDC1 , 400 MHz): 3 7.36  —  7.22 m, 9H), 5.34 (s, 1H), 5.15 (s, 1H), 3.9.1 (s, 2H), 2.38 (s, 3H). ‘ C{’H} 3  NMR (CDC1 , 100 MHz): ö 145.9, 140.4, 138.0, 137.1, 131.3, 130.5, 129.9, 129.5, 129.1, 3 128.2, 126.6, 112.5, 37.9, 20.7. HRMS (El) mlz calcd for 6 H: C, S , 240.0973; found: 240.0976. Anal. calcd for S: 16 C, 79.95; H, 6.71; found: C, 80.32; H, 6.77. H 6 C,  42  ‘H NMR (CDC1 , 400 MHz) 3 CC]  -______  9.5  9.0  9.5  8.0  7.5  7.0  6.5  6.0  .  -  6.5 5.0 4.5 ChemiaI ShOt (ppn)  4.0  35  30  2.5  2.0  1.5  1.0  0.5  , 100 MHz) 3 C NMR (CDC1 3 ‘  192  184  176  168  160  152  14  k  18  120  112  96 104 86 Chen,il Shill (pp,)  43  60  72  64  56  46  40  •  32  24  16  8  rndTp*Rh(pph) +  24h,rt,85%  Benzyl(1-benzylvinyl)sulfane (lOa): Pale yellow oil,  wa  85% yield.  Column  chromatography conditions: 20:1 hexanes:EtOAc. 1 H NMR (C , 400 MHz): D 6 6 7.27  —  7.10 (m, 1OH), 5.06 (s, 1H), 4.89 (s, 1H), 3.73 (s, 2H), 3.52 (s, 2H). ‘ C{’H} 3  , 100 MHz): 6 146.1, 139.2, 137.3, 129.7, 129.5, 129.0, 128.9, 127.6, 127.1, D 6 NMR (C 108.5, 44.3, 37.0. HRMS (El) m!z calcd for S: C 1 H 6 240.0973; found: 240.0967. Anal. calcd for S: C 1 H 6 C, 79.95; H, 6.71; found: C, 79.83; H, 6.71.  44  H NMR (C 1 , 400 MHz) D 6 I Oa  I 9.5  9.0  85  8.0  7.5  7.0  6.5  6.0  5.5 4.5 5.0 C0ernioI Shift (ppm)  4.0  3.5  3.0  2.5  2.0  1.5  1.0  0.5  c NMR (C 3 ‘ , 100 MHz) D 6 I Oa  ....-  192  184  176  168  160  152  144  136  128  120  112  104 96 88 ChemiI Shift (ppm)  A 45  80  ...  72  .  64  .  56  46  40  32  24  16  8  SH  2 ) 3 3 mol% Tp*Rh(PPh +  NC  (1:1) 3 DCE:PhCH  NC  48h,rt,88%  ha  Benzy1(3-cyanopropy1viny1su1fane (ha): Pale yellow oil, 88% yield. Column chromatography conditions: ö 7.24  —  10:1 hexanes:EtOAc. ‘H NMR (C , 400 MHz): D 6  7.09 (m, 5H), 4.90 (s, 1H), 4.71 (s, 1H), 3.64 (s, 2H), 2.01 (t, 2H, J = 7.1 Hz),  1.48 (t, 2H, J— 7.1 Hz), 1.35 (m, 2H). ‘ C{’H} NMR (C 3 , 100 MHz): ö 144.1, 137.3, D 6 129.4, 129.1, 127.8, 108.7, 36.7, 36.4, 38.7, 24.7, 15.9. HRMS (El) mlz calcd for 1 C S 5 H, N: 3 217.0925; found: 217.0926. Anal. calcd for SN: C 1 H 3 C, 71.84; H, 6.96; 5 found: C, 71.87; H, 7.12.  46  ‘H NMR (C , 400 MHz) D 6  NC-Aj’1() I Ia  !“  Chemical Shift (ppm)  , 100 MHz) D 6 C NMR (C 3 ‘ NCtQ1C) ha  4M$U$*JflI$ 192  14  6  1S  ISP  WI I$IMI*U flU flfliUJwPIVWP9flflLflflLE Nfl øMI  152144136128120112  1Ô4 86 88 Chemical Shift (ppm)  47  80  7284  5648403224168  SH  2 ) 3 3 mol% Tp*Rh(PPh +  CI  3 (1:1) DCE:PhCH 48 h, rt, 90%  I 2a  Benzyl(3-chloropropylvinyl)sulfane (12a): Pale yellow oil, 90% yield. Column chromatography conditions: 20:1 hexanes:EtOAc. 6 7.25  —  ‘H NMR (C , 400 MHz): D 6  7.07 (m, 5H), 4.99 (s, 1H), 4.76 (s, 1H), 3.69 (s, 2H), 3.17 (t, 2H, J = 6.5 Hz),  2.24 (t, 2H, J— 7.4 Hz), 1.79 (m, 2H). ‘ , 100 MHz): 6 145.3, 137.8, D 6 C{’H} NMR (C 3 129.9, 129.5, 128.2, 108.5, 44.6, 37.2, 35.4, 32.4. HRMS (El) m!z calcd for C1: 17 C 3 S 5 H, 2 228.0554; found: 228.0552. Anal. calcd for S 5 H 2 C, CJ: , C, 63.56; H, 6.67; found: C, 63.90; H, 6.69.  48  ‘H NMR (C , 400 MHz) D 6 LJ  CL—..-% I 2a  L_____ 95  90  85  80  75  70  65  60  -.__  55 55 45 ChomioI Shift (ppn)  40  30  35  25  20  15  10  05  , 100 MHz) D 6 C NMR (C 3 ‘ C.!X) I 2a  092154  176  168160  152  144  136  128  120  112  1Ô4 96 66 Chemical Shift (ppnl)  49  60  72  64  40  322416  8  SH  3rn%Tp*Rh(pph3)2 +  PhO  PhO 24 h 40°C, 33%  14a  Benzyl(phenoxymethylvinyl)sulfane (14a): Pale yellow oil, 33% yield. Column chromatography conditions: 20:1 hexanes:EtOAc, H NMR 3 (CDCJ 300 MHz): , ö 7.39  —  7.24 (m, 7H), 6.99  —  6.89 (m, 3H), 5.48 (s, 1H), 5.12 (s, 1H), 4.58 (s, 2H),  4.01 (s, 2H), 1.55 (H 0). ‘ 2 C{’H} NMR (CDC1 3 , 100 MHz): 3  159.3, 141.9, 137.6, 130.4,  129.9, 129.6, 128.3, 122.2, 115.6, 112.2, 71.6, 37.5. HRMS (ESI) m/z calcd for C 1 H S0: 6 257.1000; found: 257.0992. Anal. calcd for S0: C 1 H 6 C, 74.96; H, 6.29; found: C, 75.13; H, 6.36.  50  , 300 IvNz) 3 ‘H NMR (CDC1  PhO%Q I 4a  r”  Chemical Shift (ppm)  , 100 MHz) 3 C APT NMR (CDC1 3 I 4a  12  144  176  186  160  152  144144  i4o  i4o  12  144 96 48 Chemical Shift (ppm)  51  dv  a  44  dv  40  4b  32  24  18  4  I JSH  +  17a  —Si— 2 h, rt, 88% (A:B:C6:3:2)  I 7c  Mixture  of  benzyl(1-trimethylsilylvinyl)sulfane  (17a),  (E)-benzyl(2-  trimethylsilylvinyl)sulfane (17b), and (Z)-benzyl(2-trimethylsilylvinyl)sulfane (17c): Yellow oil, 88% yield, 6:3:2 mixture of 17a and 17b and 17c. Column chromatography conditions: 20:1 hexanes:EtOAc. ‘H NMR (CDC1 , 300 MHz): 3  7.38—7.23 (m, 27.5H:  15H: 5H 17a, 7.5H: 5H 17b and 5H: 5H 17c), 6.85 (d, 1H: 1H 17c, J— 13.25Hz), 6.55 (d, l.5H: 1H 17b, J= 17.8 Hz), 5.79 (d, l.5H: 1H 17b, J= 17.8 Hz), 5.62 (d, 1H: 1H.17c, J= 13.3 Hz), 5.45 (s, 3H: 1H 17a), 5.44 (s, 3H: 1H 17a), 3.96 (s, 9H: 6H: 2H 17a and 3H: 2H 17b), 3.90 (s, 2H: 2H 17c), 0.19 (s, 27H: 9H 17a), 0.14 (s, 9H: 9H 17c), 0.06 (s, 13.5H: 9H, 17b), 1.54 2 , 75 MHz): 6 147.7, 136.8, 129.1, 3 (H 0 C{’H} NMR (CDC1 ). 13 128.7, 127.3,  115.1, 35.6, -1.4. HRMS (El) m!z calcd for H, 1Si C S 7 2 (mixture of  isomers): 222.0899; found: 222.0896. Anal. calcd for 8 H 2 C, S Si , (mixture of isomers): C, 64.80; H, 8.16; found: C, 65.05; H, 8.21.  52  ‘H NIvIR (CDC1 , 300 MHz) 3  + +  —I I 7a  95  90  I 7c  I 7b  8:5  4.5 50 C0o S1i0 (ppn)  4.  3.5  3.0  2.5  1:5  2.0  1.0  5.5  , 75 MHz) 3 C NMR (CDC1 3 ‘  +  +  I 7c  I 7b  17a  UJJA u’iiiirnj wnRurJrInhINI( iw 192  184  176  168  160  152  144  136  128  120  .ppiiii _ii 112  104 98 88 C04n*J 51881 (ppn)  53  80  72  64  56  4  40  I—  jiiflIfl1$lI1P1I*. 32  24  16  8  5  4  os SH -  2 ) 3 3 mol% Tp*Rh(PPh  + —  EtC  QEt  3 (1:1) DCE:PhCH  —  18b +  2h,rt,68%(B:C=2:1) —  QEtS  I  I 8c  (E)-benzyl(2-ethyl carbonovinyl)sulfane (18b) Yellow oil, 40% yield. Column chromatography conditions: 20:1 hexanes:EtOAc. ‘H NMR (CDC1 , 300 MHz): 3 7.68 (d, 1H, J= 15.1 Hz), 7.35  —  7.31 (m, 5H), 5.79 (d, 1H, J= 15.5 Hz), 4.17 (q, 2H,  J= 7.3 Hz), 4.02 (s, 2H), 1.27 (t, 3H, J 7.3 Hz), 1.54 (H 0). ‘ 2 C{’H} NMR (CDC1 3 , 75 3 MHz):  165.37, 146.07, 135.63, 129.0, 128.94, 127.90, 114.63, 60.41, 36.75,  14.47. HRMS (El) rn/s calcd for S0 C 1 H : 2 2 222.0715; found: 222.0719. Anal. calcd for 4 12 C S 4 H, : 2 0 C, 64.83; H, 6.35; found: C, 64.94; H, 6.42.  54  ‘H NMR (CDC1 , 300 MHz) 3 QEt  18b  OEt  18b  Chemical Shift (ppm)  l3  192  NMR (CDC1 , 75 MHz) 3  184  176  168  160  152  144  136  19  120  112  104 96 98 Chon4eal Shift (ppm)  55  80  72  64  56  48  40  32  24  16  8  3rn%Tp*Rh(pph3)2  OSH  +  2h, rt, 75%  21a  2-((1-Phenylvinylthio)methyl)furan (21a): Yellow oil, 75% yield. Column chromatography conditions: 20:1 hexanes:EtOAc. ‘H NMR (CDC1 , 300 MHz): 3 6 7.56  —  7.53 (m, 2H), 7.39  —  7.33 (m, 4H), 6.29  —  6.27 (m, 1H), 6.10  —  6.09 (m, 1H),  5.49 (s, 1H), 5.31 (s, 1H), 3.88 (s, 2H), 1.54 (H 0). 13 2 , 75 MHz): 6 3 C{’H} NMR (CDC1 150.8, 144.4, 142.2, 139.2, 128.6, 128.5, 127.5, 113.5, 110.6, 107.8, 31.1. HRMS (El) H 3 C, S 0: , 216.0609; found: 216.0606. Anal. calcd for 2 m!z calcd for 2 H 3 C, S 0: , C, 72.19; H, 5.59; found: C, 72.45; H, 5.60.  56  , 300 MHz) 3 ‘H NMR (CDC1 21a  -  9  1  99  ••  Chemical Shift (ppm)  , 75 MHz) 3 C NMR (CDC1 3 ‘ 21a  lIEIIdfl 192  194  176  168  160  152  144  M.. . . . 1w 136  128  120  ,  112  104 06 88 Chemical Shift (ppm)  57  80  72  64  86  48  40  32  24  16  8  PhQSH  +  r__=_  rnOWOT2 .  2h,rt,70%  22a  (2-Phenoxyethyl)(1-phenylvinyl)sulfane (22a): White solid, 70% yield. Column chromatography conditions: 20:1 hexanes:EtOAc. 1 H NMR (CDC1 , 300 MHz): 3 6 7.58  —  7.55 (m, 2H), 7.38  —  7.34 (m, 2H), 7.28  —  7.23 (m, 3H), 6.96  —  6.92 (m, IH),  6.84— 6.81 (m, 2H), 5.51 (s, 1H), 5.36 (s, 1H), 4.12 (t, 2H, J= 7.1 Hz), 3.03 (t, 2H, J= 7.1 Hz), 1.54 2 C{ 3 ‘ H } NMR (CDC1 , 75 MHz): 6 158.5, 144.1, 139.3, 129.6, 3 (H 0 ). 1 128.8, 128.6, 127.5, 121.2, 114.7, 113.0, 66.4, 30.9. HRMS (El) mlz calcd for H S0: C 1 6 256.0922; found: 256.0921. Anal. calcd for H S0: C 1 6 C, 74.96; H, 6.29; found: C, 74.58; H, 6.52.  58  S  , 300 MHz) 3 ‘H NMR (CDC1  Q2a  Chonlcal Shift (ppn)  l3  NMR (CDC1 , 75 MHz) 3  22a  sr*mu ii i w. .a 12  184  176  168  160  152  14  136  128  $iZIU 0. QIIJIÜI$ :i$ 120  112  104 96 68 Chon3aI Shift (ppn)  59  80  72  64  56  46  40  32  24  16  0 0  / \  Bu0’SH  —-  2 ) 3 3 mol% Tp*Rh(PPh  s  0”Bu  (i:1) 3 DCE:PhCH 2h,rt,80%  23a  Butyl 3-(1-phenylvinylthio)propanoate (23a): Yellow oil, 80% yield. Column chromatography conditions: 20:1 hexanes:EtOAc. ‘H NMR (CDC1 , 300 MHz): 3 6 7.55  —  7.32 m, 5H), 5.51 (s, 1H), 5.27 (s, 1H), 4.09 (t, 2H, J= 6.6 Hz), 2.93 (t, 2H, J=  7.3 Hz) , 2.61 (t, 2H, J  7.3 Hz), 1.61 (m, 2H), 1.54 (H 0), 1.37 (m, 2H), 0.93 (m, 3H). 2  , 75 MHz): 3 172.0, 144.1, 139.4, 128.7, 128.6, 127.4, 112.5, 64.8, 3 C{’H} NMR (CDC1 3 ‘ 33.9, 30.8, 27.1, 19.3, 13.9. HRMS (El) rn/z calcd for 2 S0 2 H 5 C, : 0 264.1184; found: 264.1185. Anal. calcd for S0 20 C, 68.14; H, 7.62; found: C, 68.00; H, 7.36. H 5 C, : 2  60  1}{  NMR (CDC1 , 300 MHz) 3 S-’OBu  LJ  23a  ChenioI Shift (ppn)  l3  NMR (CDC1 , 75 MHz) 3 S  O”Bu 23a  192  164  176  168  160  152  144  136  128  120  112  104 96 98 Chemi6l Shift (ppm)  61  80  72  64  56  48  40  32  24  16  8  3rno1%Tp*Rh(pPh3)2 +  24 h, rt, 65%  24a  N,N-dimethyl-2-(1-phenylvinylthio)ethanamine (24a): Yellow oil, 65% yield. Column chromatography conditions: 20:1 hexanes:EtOAc and 3 % Et N. 1 3 H NMR , 400 MHz): 3 7.56 3 (CDC1  —  7.33 (m, 5H), 5.47 (s, 1H), 5.23 (s, 1H), 2.81 (t, 2H, J= 7.4  Hz), 2.57 (t, 2H, J= 7.4 Hz) , 2.25 (s, 6H). ‘ C{’H} NMR (CDC1 3 , 100 MHz): 3 145,8, 3 140.5, 129.5, 129.3, 128.2, 112.1, 59.1, 46.2, 30.8. HRMS (El) mlz calcd for NS: C 1 H 2 7 207.1082; found: 207.1078.  62  ‘H NMR (CDC1 , 300 MHz) 3  24a  ChmiooI Shift (ppm)  , 100 MHz) 3 c NMR (CDC1 3 ‘  LJ  24a  — 192  184  176  168  180  102  144  136  128  120  112  104 96 88 Chemical Shift (ppm)  63  80  72  64  86  48  40  32  24  16  8  CO 3 H 3 +  O:3)2  H3CO-Q-1.1 equivoerS  24h,rt,80%  23a  3 OCH  1,2-Bis(1-(4-methoxyphenyl)vinylthio)hexane (34a): Yellow oil, 80% yield. Column chromatography conditions: 20:1 hexanes:EtOAc. ‘H NMR (C , 400 MHz): D 6 6 7.60  —  7.56 (m, 4H), 6.76  (t, 4H, J  —  6.73 (m, 4H), 5.41 (s, 2H), 5.13 (s, 2H), 3.30 (s, 6H), 2.50  7.3 Hz), 1.45 (quin, 4H, J = 7.3 Hz), 1.13 (quin, 4H, J = 3.7 Hz). ‘ C{’H} 3  NMR (C , 100 MHz): 6 160.8, 145.9, 133.1, 129.1, 114.5, 109.6, 55.2, 32.6, 29.1, D 6 29.0. HRMS (El) mlz calcd for 2 S 2 C 3 H 4 02: 414.1686; found: 414.1687. Anal. calcd for 0 S 2 C 3 H 2 4 02: C, 69.52; H, 7.29; found: C, 69.20; H, 7.31. 0  64  ‘H NIVIR (C , 400 MHz) D 6  28a  OCH  ChmiI Shift (ppm)  13,  i-  L- P4.LVLL  i  KTT  \  I VU IVLf1Z)  CO 3 H  XySsIQ 28a  3 OCH  ..  192  184  176  168  160  162  144  136  129  120  112  104 96 88 ChmmI Shift (ppm)  65  80  72  64  56  48  40  32  24  16  8  2 (93 mg, 0.1 mmol) in ) 3 Synthesis of complex II. In glove box, a solution of Tp*Rh(PPh toluene (1 mL) were combined in the glove box in a 5 mL vial equipped with a screw cap and a magnetic stir bar. 2-pyridylacetylene (0.1 mL, 1.0 mmol) was added by syringe to the solution. The mixture was stirred for 2 h at room temperature, followed by layering with 2 mL hexanes. After 2 days, brown crystals formed. The solution was decanted, and the crystals were washed with 2 x 1 mL of hexanes. The product was dried under reduced pressure to give 50 mg (65 400 MHz) at 25 °C: 8 8.19 (d, lH, J 7.20 (m, 6H), 7.70  —  %) of an brown crystalline solid. ‘H NMR 2 C1 (CD , 3.9 Hz) 7.60 (m, 6H),7.42  —  7.33 (m, 4H), 7.24  6.90 (m, 2H), 5.71 (d, 2H, J= 8.8 Hz), 5.17 (s, 1H), 2.72 (s, 3H),  2.50 (s, 3H), 2.30 (s, 3H), 2.25 (s, 3H), 1.44 (s, 3H), 1.37 (s, 3H), 6-14.68 (q, lH, 20.5  HZ,JP..H  —  JRII-H=  17.6 Hz), B-H not observed. ‘ C{’H} NMR 2 3 C1 100 MHz): 6 154.5, (CD ,  150.8, 149.8, 147.8, 145.5, 144.5, 135.9, 135.8, 135.6, 133.8, 133.4, 130.5, 128.2, 128.1, 126.1, 119.7, 107.5, 106.3, 106.1, 16.5, 13.2, 12.9, 12.1. 31 P{’H} NMR 2 C1 121 (CD , MHz): 6 37.69  (JR1,p  130.8 Hz). HRMS (El) miz calcd for 7 BN C 4 H P Rh: 0 765.2387; 2  found: 765.2389. X-Ray crystal structure of complex II: Measurement for complexes II was made on a Bruker X8 APEX II diffractometer with graphite monochromated Mo-Ka radiation. Data were collected in a series of 0 and co scans and subsequently processed with the 24 software package. Data were corrected for absorption effects using the Bruker SAINT multiscan technique (SADABS). 25 Data were corrected for by Lorentz and polarization 26 and refined using SHELXTL. effects. The structure was solved using direct methods 27 For complexe II all non-hydrogen atoms were refined anisotropically, whereas all hydrogen atoms were placed in calculated positions and not refined, except for B-H  66  hydrogen which was located in difference maps and refined isotropically. The material crystallizes with both toluene and hexane in the lattice. In this ease, there was a 1:2 mixture of toluene and hexane occupying the same space in the asymmetric unit. Mild restraints were employed to maintain reasonable geometries for both solvent molecules. Full details for complex II are presented in the Appendix.  67  ‘H NMR 2 C1 400 MHz) (CD ,  Complex II  I 9  9  7  6  4  5  3  2  I  0  -l  -2 -3 -4 Chen1 ShWt (ppm)  -5  -7  -6  -8  -9  -10  -11  CI 100 MHz) (CD , c NMR 2 3 ‘  [. -  I 192  184  176  168  160  152  144  .ljj 128  -13  -14  .15  Complex II  p 136  -12  120  112  •1  104 96 88 CmniI Shtppm)  68  Mflrr1II$I, 80  72  84  56  48  40  32  24  16  8  -16  Chapter 3  —  Summary, Conclusons and Future Work  3.1 Summary and Conclusions The goal of this thesis project was to explore the substrate scope and limitations of Tp*Rh(PPh as the catalyst. 3 2 ) Tp*Rh(PPh was found to 2 ) alkyne hydrothiolation using 3 be effective for a variety of thiols and alkynes, including both terminal and internal alkynes. Most of the reactions gave good-to-excellent yields, and the branched isomer was favored in most cases. Electronic substitution of substituted phenyl acetylenes had little influence on regioselectivity, but had a great impact on the reaction efficiency and yields. Aliphatic alkynes need longer reaction time to complete reaction compared to aryl alkynes. A wide range of functional groups were tolerated, including halides, amines, nitriles, amines, ethers, esters and silanes. Alkoxy groups with the ability to coordinate with rhodium slowed down the catalytic turnover and lower the yield. Strongly coordinating groups, such as pyridine, totally precluded catalysis. The regioselectivity of the catalyst was reversed when electronically activated alkynes, i.e., those that undergo Michael addition, were used. Hydrothiolation using internal alkynes was much more difficult and needed longer reaction time and higher reaction temperature for completion.  69  3.2 Future Work Further attention is warranted in several areas. In a few reactions, some byproducts were formed (about 5-10%). Although efforts to date have been unsuccessful in unequivocally determining the identity of the byproducts, larger scale reactions could provide sufficient material for isolation and characterization. Moreover, the product identity could provide some mechanistic clues. On the other hand, a detailed mechanistic picture could point out how to minimize the byproduct and also give more information about the scope and limitation. Such mechanistic work is currently underway.’ ’ 31 We have demonstrated that the products of the hydrothiolation using n-propanethiol are suitable for Kumada cross-coupling to generate 1,1-disubstituted olefins. Other functionalization of 1,1 -disubstituted vinyl sulfide could also be studied, such as Diels Alder reactions. In addition, hydrothiolation could be used as a key step in the synthesis of some sulfur containing natural products and drug molecules , such as Emtricitabine, 28 Eletriptan, and Ertapenem (see Figure 3.1). 0 NH  H  OH  HOQ N OH  H  Figure 3.1. Emtricitabine, Eletriptan, and Ertapenem  The Tp* ligand has shown unique properties in rhodium catalyzed alkyne hydrothiolation. It would be interesting to synthesize other metal complexes with this ligand. These new complexes may have different reactivity in hydrothiolation, as well as  70  other reactions, such as asymmetric hydrogenation, cyclotrimerization and Diels-Alder reactions, In addition, other bidentate or tridentate ligands can also be used to form new rhodium complexes. Those new ligands may provide new selectivities in hydrothiolations. 2 in S-H and P-H bond activation ) 3 After having demonstrated the use of Tp*Rh(PPh reactions, activation of H-X bonds (such as X  =  0) could be paid more attention. For  example, the intermolecular alkyne hydroalkoxylation using rhodium complex could be an interesting research topic.  On the other hand,  after investigating alkyne  hydrothiolation, the stereoselective alkene hydrothiolation reactions also have a good potential to study.  71  References (1)  For examples of sulfur compounds as synthetic precursors or reagents for methodology, see: (a) Metzner, P.; Thuillier, A. In Sulfur Reagents in Organic Synthesis; Academic Press: London, 1994, 200. (b) Bratz, M.; Bullock, W. H.; Overman, L. E.; Takemoto, T. J. Am. them. Soc. 1995, 11/, 5958-5966. (c) Stiefel, E. I.; Matsumoto, K., Eds.; In Transition Metal Sulfur Chemistiy: Biological and Industrial Signflcance; ACS Symposium Series 653; ACS: Washington, DC, 1996, 358. (d) Vedüla, M. S.; Pulipaka, A. B.; Venna, C.; Chintakunta, V. K.; Jinnapally, S.; Kattuboina, V. A.; Vallakati, R. K.; Basetti, V.; Akella, V.; Rajgopal, S.; Reka, A. K.; Teepireddy, S. K.; Mamnoor, P. 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(24) Bruker SAINT software package, version 7.03A; Bruker AXS Inc.: Madison, WI, 1997-2003. (25) Bruker SAINT software package, Version 2.10; Bruker AXS Inc.: Madison, WI, 2003. (26) Altomare, A.; Burla, M. C.; Camalli, M.; Cascarano, G. L.; Giacovazzo, C.; Guagliardi, A.; Molitemi, A. G. G.; Polidori, G.; Spagna, R. I Appi. Cryst. 1999, 32, 115-119. (27) Bruker SAINT software package, Version 5.1; Bruker AXS Inc.: Madison, WI, 1997. (28)Fernández, F.; Khiar, N. Chem. Rev. 2003, 103, 365 1-3705.  76  Appendix: X-ray Crystallographic Data for Complex II A. Crystal Data Empirical Formula Formula Weight Crystal Color, Habit Crystal Dimensions Crystal System Lattice Type Lattice Parameters  BN C 4 H P 7 0 2 Rh 765.50 yellow, prism 0.26 X 0.44 X 0.50 mm orthrhombic primitive a = 15.85 1(2) A ci. = 90.0 b= 19.184(3)A =9O.O c=23.951(4)A y=9O.O V = 4667.9(8) A 3 P bca (#6 1) 8 3 1.396g/cm 3168.00 5.53cm’  Space Group Z value Dcalc F000 .i(MoKa) B. Intensity Measurements Diffractometer Radiation  Bruker X8 APEX II MoKc ( = 0.7 1073 A) graphite monochromated 1071 exposures @ 5.0 seconds 36.00 mm 56.0° Total: 67640 Unique: 8786 (R 1 = 0.025) Absorption (T 1 = 0.803, Tmax= 0.866); Lorentz-polarization  Data Images Detector Position 2Omax No. of Reflections Measured Corrections  C. Structure Solution and Refmement Structure Solution Refmement Function Minimized Least Squares Weights Anomalous Dispersion No. Observations (I>0.OOa(1)) No. Variables Reflection/Parameter Ratio  Direct Methods (S1R97) Full-matrix least-squares on F 2 w (Fo 2 Fe ) 2 ( w=1/(a ) 2 +(0.0252P) Fo + 6.3229P) All non-hydrogen atoms 8786 465 18.89 —  77  Residuals (refined on F , all data): Ri; wR2 2 Goodness of Fit Indicator No. Observations (I>2.OOa(I)) Residuals (refined on F): RI; wR2 Max ShiftlError in Final Cycle Maximum peak in Final Diff. Map Minimum peak in Final Diff. Map  78  0.034; 0.066 1.08 8528 0.024; 0.058 0.00 0.37 e/A 3 -0.45 e/A 3  Table 1. Atomic Coordinates (x 1O) and Equivalent Isotropic Displacement Parameters (A x 1O) Atom C(1) C(2) C(3) C(4) C(5) C(6) C(7) C(8) C(9) C(10) C(11) C(12) C(13) C(14) C(15) C(16) C(17) C(18) C(19) C(20) C(21) C(22) C(23) C(24) C(25) C(26) C(27) C(28) C(29) C(30) C(31) C(32) C(33) C(34) C(35) C(36) C(37) C(38) C(39) C(40) N(1)  X 3595(1) 3929(1) 3465(1) 4042(1) 3909(1) 7592(1) 7058(1) 7088(1) 6529(1) 6290(1) 7217(1) 6883(1) 7009(1) 6576(1) 6504(1) 5451(1) 4991(1) 4926(1) 5326(1) 5784(1) 5845(1) 6200(1) 5907(1) 6402(1) 7189(1) 7481(1) 6985(1) 4519(1) 3845(1) 3094(1) 3002(1) 3671(1) 4428(1) 5683(1) 5547(1) 5323(1) 4368(1) 4811(1) 5562(1) 5827(1) 4756(1)  Y 1859(1) 1913(1) 1887(1) 1909(1) 1919(1) 3523(1) 3235(1) 3391(1) 2945(1) 2875(1) 661(1) 779(1) 381(1) 707(1) 504(1) 3915(1) 3753(1) 4232(1) 4875(1) 5037(1) 4562(1) 3632(1) 4228(1) 4560(1) 4299(1) 3703(1) 3370(1) 3282(1) 3669(1) 371 5(1) 3375(1) 2993(1) 2948(1) 1740(1) 1443(1) 1054(1) 825(1) 261(1) 98(1) 500(1) 1961(1)  79  Z 6238(1) 6819(1) 7317(1) 7743(1) 8362(1) 6858(1) 7313(1) 7883(1) 8142(1) 8746(1) 6221(1) 6797(1) 7278(1) 7700(1) 8301(1) 6643(1) 7125(1) 7557(1) 7518(1) 7047(1) 6608(1) 5559(1) 5282(1) 4888(1) 4758(1) 5016(1) 5414(1) 5750(1) 5962(1) 5664(1) 5157(1) 4944(1) 5234(1) 5812(1) 5374(1) 4883(1) 4190(1) 3996(1) 4256(1) 4703(1) 6936(1)  U(eq) 26(1) 21(1) 25(1) 23(1) 32(1) 26(1) 22(1) 28(1) 26(1) 40(1) 29(1) 23(1) 28(1) 24(1) 35(1) 20(1) 23(1) 30(1) 33(1) 31(1) 26(1) 21(1) 30(1) 36(1) 34(1) 33(1) 26(1) 20(1) 24(1) 29(1) 32(1) 30(1) 25(1) 19(1) 23(1) 22(1) 37(1) 35(1) 33(1) 27(1) 19(1)  N(2) N(3) N(4) N(5) N(6) N(7) Rh(1) B(1) P(i)  4819(1) 6490(1) 6183(1) 6393(1) 6199(1) 4598(1) 5973(1) 5683(1) 5545(1)  1941(1) 2726(1) 2542(1) 1324(1) 1281(1) 1226(1) 2226(1) 1856(1) 3240(1)  80  7510(1) 7228(1) 7741(1) 6923(1) 7483(1) 4623(1) 6507(1) 7788(1) 6105(1)  20(1) 19(1) 21(1) 19(1) 20(1) 31(1) 15(1) 21(1) 17(1)  Table 2. Bond Lengths Atoms C(1)-C(2) C(1)-H(1A) C(1 )-H(1 B) C(1)-H(1 C) C(2)-N(1) C(2)-C(3) C(3)-C(4) C(3)-H(3) C(4)-N(2) C(4)-C(5) C(5)-H(5A) C(5)-H(5B) C(5)-H(5C) C(6)-C(7) C(6)-H(6A) C(6)-H(6B) C(6)-H(6C) C(7)-N(3) C(7)-C(8) C(8)-C(9) C(8)-H(8) C(9)-N(4) C(9)-C(1 0) C(10)-H(1OA) C(1 0)-H(1 OB) C(1 0)-H(1 OC) C(1 1)-C(12) C( 11 )-H(1 1A) C(1 1)-H(1 1B) C(1 1)-H(1 1C) C( 1 2)-N(5) C(12)-C(13) C(1 3)-C(1 4) C(1 3)-H(1 3) C(14)-N(6) C(1 4)-C(1 5) C(1 5)-H(1 5A) C(15)-H(15B) C(1 5)-H(1 5C) C(1 6)-C(21) C(16)-C(17) C(16)-P(1)  (A) Length (A) 1.492(2) 0.98 0.98 0.98 1.343(2) 1.401(2) 1.371(3) 0.95 1.354(2) 1.497(3) 0.98 0.98 0.98 1.488(2) 0.98 0.98 0.98 1.343(2) 1.399(3) 1.379(3) 0.95 1.351(2) 1.501(3) 0.98 0.98 0.98 1.494(3) 0.98 0.98 0.98 1.338(2) 1.397(2) 1.372(3) 0.95 1.355(2) 1.497(3) 0.98 0.98 0.98 1.392(2) 1.399(2) 1.8330(17)  Atoms C(21)-H(21) C(22)-C(27) C(22)-C(23) C(22)-P(1) C(23)-C(24) C(23)-H(23) C(24)-C(25) C(24)-H(24) C(25)-C(26) C(25)-H(25) C(26)-C(27) C(26)-H(26) C(27)-H(27) C(28)-C(29) C(28)-C(33) C(28)-P( 1) C(29)-C(30) C(29)-H(29) C(30)-C(3 1) C(30)-H(30) C(31)-C(32) C(3 1)-H(3 1) C(32)-C(33) C(32)-H(32) C(33)-H(33) C(34)-C(35) C(34)-Rh(1) C(35)-C(36) C(36)-N(7) C(36)-C(40) C(37)-N(7) C(37)-C(38) C(37)-H(37) C(38)-C(39) C(38)-H(3 8) C(39)-C(40) C(3 9)-H(39) C(40)-H(40) N(1)-N(2) N(1 )-Rh(1) N(2)-B(1) N(3)-N(4)  81  Length (A) 0.95 1.385(2) 1.401(2) 1.8334(17) 1.382(3) 0.95 1.380(3) 0.95 1.378(3) 0.95 1.393(3) 0.95 0.95 1.396(2) 1.398(2) 1.8374(17) 1.392(2) 0.95 1.386(3) 0.95 1.387(3) 0.95 1.389(3) 0.95 0.95 1.212(2) 1.9627(17) 1.437(2) 1.348(2) 1.398(2) 1.342(3) 1.371(3) 0.95 1.380(3) 0.95 1.383(3) 0.95 0.95 1.3773(19) 2.2448(14) 1.531(2) 1.368(2)  C(17)-C(18) C(1 7)-H(1 7) C(18)-C(19) C(18)-H(18) C(1 9)-C(20) C(1 9)-H(1 9) C(20)-C(21) C(20)-H(20)  1.388(2) 0.95 1.391(3) 0.95 1.375(3) 0.95 1.395(3) 0.95  N(3)-Rh(1) N(4)-B(1) N(5).N(6) N(5)-Rh(1) N(6)-B(1) Rh(1 )-P(1) Rh(1)-H(1) B(1)-H(2)  82  2.1386(14) 1.541(2) 1.379(2) 2.1037(14) 1.555(2) 2.2732(5) 1.46(2) 1.068(19)  Table 3. Bond Angles fl Atoms C(2)-C(1)-H(1A) C(2)-C(1)-H(1B) H(1A)-C(1)-H(1B) C(2)-C(1)-H(1C) H(1A)-C(1)-H(1C) H(1B)-C(1)-H(1C) N(1)-C(2)-C(3) N(1)-C(2)-C(1) C(3)-C(2)-C(1) C(4)-C(3)-C(2) C(4)-C(3)-H(3) C(2)-C(3)-H(3) N(2)-C(4)-C(3) N(2)-C(4)-C(5) C(3)-C(4)-C(5) C(4)-C(5)-H(5A) C(4)-C(5)-H(5B) H(5A)-C(5)-H(5B) C(4)-C(5)-H(5C) H(5A)-C(5)-H(5C) H(5B)-C(5)-H(SC) C(7)-C(6)-H(6A) C(7)-C(6)-H(6B) H(6A)-C(6)-H(6B) C(7)-C(6)-H(6C) H(6A)-C(6)-H(6C) H(6B)-C(6)-H(6C) N(3)-C(7)-C(8) N(3)-C(7)-C(6) C(8)-C(7)-C(6) C(9)-C(8)-C(7) C(9)-C(8)-H(8) C(7)-C(8)-H(8) N(4)-C(9)-C(8) N(4)-C(9)-C(10) C(8)-C(9)-C(10) C(9)eC(10)H(10A) C(9)-c(10)-H(1OB) H(1)4D()10)  Angle (°) 109.5 109.5 109.5 109.5 109.5 109.5 109.71(15) 123.06(16) 127.16(15) 106.39(15) 126.8 126.8 107.48(15) 122A6(16) 130.04(16) 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.13(16) 122.66(15) 128.07(16) 106.49(15) 126.8 126.8 107.22(16) 122.18(17) 130.60(17) 109.5 109.5  Atoms C(26)-C(25)-C(24) C(26)-C(25)-H(25) C(24)-C(25)-H(25) C(25>C(26)eC(27) C(25)-C(26)-H(26) C(27)-C(26)-H(26) C(22)-C(27)-C(26) C(22)-C(27)-H(27) C(26)-C(27)-H(27) C(29)-C(28)-C(33) C(29)-C(28)-P(1) C(33)-C(28)-P(1) C(30)-C(29)-C(28) C(30)-C(29)-H(29) C(28)-C(29)-H(29) C(31)-C(30)-C(29) C(31)-C(30)-H(30) C(29)-C(30)-H(30) C(30)-C(31)-C(32) C(30)-C(31)-H(31) C(32)-C(31)-H(31) C(31)-C(32)-C(33) C(31)-C(32)-H(32) C(33)-C(32)-H(32) C(32)-C(33)-C(28) C(32)-C(33)-H(33) C(28)-C(33)-H(33) C(35)-C(34)-Rh(1) C(34)-C(35)-C(36) N(7)-C(36)-C(40) N(7)-C(36)-C(35) C(40)-C(36)-C(35) N(7)-C(37)-C(38) N(7)-C(37)-H(37) C(38)-C(37)-H(37) C(37)-C(38)-C(39) C(37>C(38>H(38) C(39)-C(38)-H(38)  Angle (°) 120.18(18) 119.9 119.9 119.88(18) 120.1 120.1 120.72(17) 119.6. 119.6 119.08(16) 122.12(13) 118.70(13) 120.09(17) 120 120 120.64(18) 119.7 119.7 119.37(17) 1203 120.3 120.58(1 8) 119.7 119.7 12021(17) 119.9 119.9 176.59(15) 174.47(18) 121.96(16) 117.47(16) 120.51(16) 125.08(19) 1173 117.5 117.89(18) 121.1 121.1  109.5  C(38)-C(39)-C(40)  118.96(19)  C(9)-C(10)-H(1OC) H(1>COO>  109.5  C(38)-C(39)-H(39)  120.5  109.5  C(40)-C(39)-H(39)  120.5  83  H( 1 OB)-C( 10)H(1OC) C(1 2)-C(1 1)H(1 IA) C(1 2)-C(1 1)H(11B) H(1 1A)-C(1 1)H(11B) C(12)—C(1 1)— H(11C) H(1 1A)—C(1 1)— H(1IC) H(11B)-C(11)H(11C) N(5)-C(12)-C(13) N(5)-C(12)-C(1 1) C(13)-C(12)-C(1 1) C(14)-C( 1 3)-C(12) C(14)-C(13)-H(13) C(1 2)-C(1 3)-H(1 3) N(6)-C(14)-C(1 3) N(6)-C(14)-C(15) C(13)-C(14)-C(1 5) C(14)-C(15)H(15A) C(1 4)-C(1 5)H(15B) H(1 5A)-C(1 5)H(15B) C(14)-C(1 5)H(15C) H(1 5A)-C(1 5)H(15C) H(1 5B)-C(1 5)H(15C) C(2 1 )-C( 1 6)-C(1 7) C(2 1 )-C(1 6)-P(1) C(1 7)-C(1 6)-P( 1) C(1 8)-C(1 7)-C(1 6) C(1 8)-C(1 7)-H(1 7) C( J. 6)-C( 1 7)-H( 17) C(1 7)-C(1 8)-C(1 9) C(1 7)-C(1 8)-H(1 8) C(19)-C(1 8)-H(1 8) C(20)-C(1 9)-C(1 8) C(20)-C( 1 9)-H(1 9)  109.5  C(39)-C(40)-C(36)  119.37(18)  109.5  C(39)-C(40)-H(40)  120.3  109.5  C(36)-C(40)-H(40)  120.3  109.5  C(2)-N(1)-N(2)  106.12(13)  109.5  C(2)-N(1)-Rh(1)  139.34(12)  109.5  N(2)-N(1)-Rh(1)  113.58(10)  109.5  C(4)-N(2)-N(1)  110.25(14)  108.94(16) 122.16(16) 128.89(16) 106.61(15) 126.7 126.7 108.03(16) 123.13(17) 128.84(17)  C(4)-N(2)-B(1) N(1)-N(2)-B(1) C(7)-N(3)-N(4) C(7)-N(3)-Rh(1) N(4)-N(3)-Rh(1) C(9)-N(4)-N(3) C(9)-N(4)-B(1) N(3)-N(4)-B(1) C(12)-N(5)-N(6)  128.97(15) 120.13(13) 106.80(13) 134.92(12) 118.21(10) 110.32(14) 130.27(15) 117.97(13) 107.51(13)  109.5  C(12)-N(5)-Rh(1)  136.08(12)  109.5  N(6)-N(5)-Rh(1)  116.10(10)  109.5  C(14)-N(6)-N(5)  108.90(14)  109.5  C(14)-N(6)-B(1)  128.90(15)  109.5  N(5)-N(6)-B(1)  122.05(13)  109.5  C(37)-N(7)-C(36)  116.69(17)  118.74(16) 123.47(13) 117.72(12) 120.46(16) 119.8 119.8 120.20(18) 119.9 119.9 119.73(17) 120.1  C(34)-Rh(1 )-N(5) C(34)-Rh( 1 )-N(3) N(5)-Rh(1 )-N(3) C(34)-Rh(1 )-N(1) N(5)-Rh(1 )-N(1) N(3)-Rh(1 )-N(1) C(34)-Rh(1 )-P(1) N(5)-Rh( 1 )-P(1) N(3)-Rh(1)-P(1) N(1)-Rh(1)-P(1) C(34)-Rh( 1 )-H(1)  94.85(6) 171.02(6) 82.29(5) 94.55(6) 82.46(5) 93.52(5) 88.72(5) 176.42(4) 94.14(4) 97.51(4) 83 .8(9)  84  C(1 8)-C(i 9)-H(1 9) C(1 9)-C(20)-C(2 1) C(1 9)C(20)-H(20) C(2J )-C(20)-H(20) C(1 6)-C(2 1 )-C(20) C(16)-C(21)H(21) C(20)-C(2 1)-H(2 1) C(27)-C(22)-C(23) C(27)-C(22)-P(1) C(23)-C(22)-P(1) C(24)-C(23)-C(22) C(24)-C(23)-H(23) C(22)-C(23)-H(23) C(25)-C(24)-C(23) C(25)-C(24)-H(24) C(23)-C(24)-H(24)  120.1 120.45(17) 119.8 119.8 120.40(17) 119.8 1 19.8 118.48(16) 122.53(13) 118.97(13) 120.63(18) 119.7 119.7 120.06(19) 120 120  N(5)-Rh(1)-H(1) N(3)-Rh(1 )-H(1) N(1)-Rh(1)-H(1) P(1)-Rh(1)-H(1) N(2)-B( 1 )-N(4) N(2)-B(1)-N(6) N(4)-B(1 )..N(6) N(2)-B(1 )-H(2) N(4)-B(1)-H(2) N(6)-B(1)-H(2) C( 1 6)-P(1 )-C(22) C( 1 6)-P( 1 )-C(28) C(22)-P(1)-C(28) C(1 6)-P(1 )-Rh(1) C(22)-P(1)-Rh(1) C(28)-P(1 )-Rh( 1)  85  92.1(8) 87.8(9) 174.1(8) 88.1(8) 109.69(14) 110.01(14) 107.54(14) 111.2(10) 109.8(10) 108.5(10) 104.94(8) 102.88(8) 98.75(8) 109.33(6) 118.96(6) 119.92(5)  Table 4. Anisotropic Displacement Parameters Atom C(1) C(2) C(3) C(4) C(5) C(6) C(7) C(8) C(9) C(10) C(11) C(12) C(13) C(14) C(15) C(16) C(17) C(18) C(19) C(20) C(21) C(22) C(23) C(24) C(25) C(26) C(27) C(28) C(29) C(30) C(31) C(32) C(33) C(34) C(35) C(36) C(37) C(38) C(39) C(40) N(1) N(2)  U 1 1 21(1) 18(1) 18(1) 22(1) 30(1) 22(1) 19(1) 26(1) 24(1) 40(1) 26(1) 19(1) 25(1) 22(1) 39(1) 17(1) 24(1) 32(1) 37(1) 31(1) 24(1) 21(1) 24(1) 35(1) 32(1) 24(1) 25(1) 18(1) 21(1) 20(1) 24(1) 31(1) 25(1) 18(1) 23(1) 25(1) 37(1) 47(1) 42(1) 28(1) 18(1) 20(1)  U 2 2 27(1) 16(1) 24(1) 19(1) 37(1) 24(1) 20(1) 30(1) 31(1) 54(1) 27(1) 19(1) 19(1) 21(1) 34(1) 19(1) 20(1) 32(1) 28(1) 20(1) 21(1) 22(1) 31(1) 35(1) 43(1) 47(1) 31(1) 19(1) 22(1) 28(1) 38(1) 35(1) 27(1) 18(1) 22(1) 23(1) 45(1) 38(1) 29(1) 27(1) 20(1) 20(1)  U 3 3 29(1) 28(1) 32(1) 27(1) 27(1) 33(1) 28(1) 29(1) 24(1) 26(1) 32(1) 30(1) 38(1) 30(1) 33(1) 24(1) 25(1) 25(1) 33(1) 42(1) 32(1) 20(1) 35(1) 38(1) 26(1) 29(1) 23(1) 22(1) 29(1) 39(1) 35(1) 24(1) 23(1) 21(1) 25(1) 19(1) 28(1) 20(1) 29(1) 24(1) 19(1) 19(1)  86  (A x 1O) U 2 3 2(1) 1(1) 2(1) 1(1) 0(1) -2(1) -4(1) -10(1) •.8(1) -13(1) -4(1) -2(1) 3(1) 7(1) 13(1) -1(1) 0(1) -6(1) -12(1) -6(1) 0(1) 2(1) 11(1) 16(1) 7(1) 3(1) 3(1) 5(1) 2(1) 5(1) 12(1) 3(1) 2(1) 1(1) -2(1) 0(1) -1(1) -6(1) -8(1) -3(1) 1(1) 1(1)  U’ 3 -4(1) -2(1) 3(1) 5(1) 9(1) -1(1) -4(1) -4(1) -5(1) 1(1) 0(1) -3(1) —5(1) -6(1) -5(1) 0(1) 1(1) 4(1) -1(1) -1(1) 3(1) 2(1) 7(1) 4(1) 7(1) 8(1) 3(1) -1(1) 0(1) -1(1) -9(1) -6(1) 0(1) -1(1) -1(1) 1(1) -11(1) 0(1) 8(1) 1(1) —1(1) 1(1)  2 U’ -2(1) -1(1) 1(1) 5(1) 1(1) -5(1) -1(1) -11(1) 6(1) 0(1) 3(1) -2(1) 3(1) 2(1) -1(1) 1(1) 3(1) -3(1) -2(1) -3(1) 3(1) -3(1) -11(1) 0(1) 2(1) -1(1) -1(1) 3(1) -2(1) -4(1) 0(1) 0(1) 0(1) -4(1) -5(1) -15(1) -4(1) -1(1) —1(1) -1(1)  N(3) N(4) N(5) N(6) N(7) Rh(1) B(1) P(1)  18(1) 21(1) 19(1) 19(1) 31(1) 14(1) 21(1) 16(1)  18(1) 23(1) 19(1) 21(1) 34(1) 14(1) 23(1) 16(1)  20(1) 19(1) 20(1) 21(1) 29(1) 16(1) 20(1) 18(1)  87  -1(1) -2(1) 0(1) 3(1) -4(1) —1(1) 1(1) 0(1)  -2(1) .2(1) —1(1) -2(1) -7(1) .1(1) -2(1) 2(1)  •1(i) 1(1) 0(1) -1(1) 2(1) —1(1) 0(1) 0(1)  Table 5. Torsional Angles (°) Atoms N( 1 )-C(2)-C(3)-C(4) C(1)-C(2)-C(3)-C(4) C(2)-C(3)-C(4)-N(2) C(2)-C(3)-C(4)-C(5) N(3)-C(7)-C(8)-C(9) C(6)-C(7)-C(8)-C(9) C(7)-C(8)-C(9)-N(4) C(7)-C(8)-C(9)-C( 10) N(S)-C( 1 2)-C( 1 3)-C( 14) C(1 1 )-C(1 2)-C(1 3)-C(1 4) C(1 2)-C( 1 3)-C(1 4)-N(6) C(1 2)-C(1 3)-C(14)-C(1 5) C(2 1)-C(1 6)-C(1 7)-C(1 8) P(1 )-C(1 6)-C(1 7)-C(1 8) C(1 6)-C(1 7)-C(I 8)-C(1 9) C( 1 7)-C(i 8)-C( 1 9)-C(20) C(1 8)-C( 1 9)-C(20)-C(2 1) C( 1 7)-C(1 6)-C(2 1 )-C(20) P(1)-C(1 6)-C(2 1 )-C(20) C(1 9)-C(20)-C(2 1 )-C( 16) C(27)-C(22)-C(23)-C(24) P( 1 )-C(22)-C(23)-C(24) C(22)-C(23)-C(24)-C(25) C(23)-C(24)-C(25)-C(26) C(24)-C(25)-C(26)-C(27) C(23)-C(22)-C(27)-C(26) P(1)-C(22)-C(27)-C(26) C(25)-C(26)-C(27)-C(22) C(3 3)-C(28)-C(29)-C(30) P(1 )-C(28)-C(29)-C(30) C(28)-C(29)-C(3 0)-C(3 1) C(29)-C(3 0)-C(3 1 )-C(32) C(30)-C(3 1 )-C(32)-C(33) C(3 1)-C(32)-C(33)-C(28) C(29)-C(28)-C(33)-C(32) P(1 )-C(28)-C(33)-C(32) Rh(1 )-C(34)-C(35)-C(36) C(34)-C(3 5)-C(3 6)-N(7) C(34)-C(3 5)-C(36)-C(40) N(7)-C(3 7)-C(3 8)-C(3 9) C(3 7)-C(3 8)-C(3 9)-C(40) C(3 8)-C(3 9)-C(40)-C(36)  Angle .1.04(19) 175.87(16) -0.43(19) 177.82(18) 1.3(2) -174.33(17) 0.0(2) -179.5(2) 0.0(2) 179.58(17) 0.1(2) -179.57(18) 0.3(3) 177.40(14) -0.7(3) 0.4(3) 0.3(3) 0.4(3) -176.S2(14) -0.7(3) -2.1(3) 176.69(16) 0.7(3) 0.8(3) -1.0(3) 1.9(3) -176.85(15) -0.3(3) 0.4(2) 176.73(13) 0.5(3) -0.8(3) 0.1(3) 0.8(3) -1.0(3) -177.0(14) 149.7(18) 75(2) -103(2) -1.4(3) 0.9(3) 0.8(3)  Atoms Rh(l )-N(5)-N(6)-C( 14) C(1 2)-N(5)-N(6)-B(1) Rh(1 )-N(5)-N(6)-B( 1) C(38)-C(37)-N(7). C(36) C(40)-C(36)-N(7)-C(3 7) C(3 5)-C(36)-N(7)-C(3 7) C(3 5)-C(34)-Rh( 1)-N(S) C(3 S)-C(3 4)-Rh( 1 )-N(3) C(3 5)-C(34)-Rh( 1 )-N(1) C(3 5)-C(34)-Rh(1 )-P(1) C(1 2)-N(5)-Rh( 1 )-C(34) N(6)-N(5)-Rh(1 )-C(34) C(1 2)-N(5)-Rh(1 )-N(3) N(6)-N(S)-Rh(1 )-N(3) C(1 2)-N(5)-Rh(1 )-N(1) N(6)-N(5)-Rh(1 )-N(1) C( 1 2)-N(S)-Rh(1 )-P(1) N(6)-N(5)-Rh( 1 )-P( 1) C(7)-N(3)-Rh(1)-C(34) N(4)-N(3)-Rh( 1 )-C(34) C(7)-N(3)-Rh( 1 )-N(5) N(4)-N(3)-Rh( 1 )-N(5) C(7)-N(3)-Rh( 1 )-N(1) N(4)-N(3)-Rh( 1 )-N(1) C(7)-N(3)-Rh( 1 )-P( 1) N(4)-N(3)-Rh(1 )-P(1) C(2)-N(1 )-Rh(1)-C(34) N(2)-N( 1 )-Rh( 1 )-C(34) C(2)-N( 1 )-Rh(1 )-N(5) N(2)-N(1)-Rh(1 )-N(S) C(2)-N( 1 )-Rh( 1 )-N(3) N(2)-N( 1 )-Rh( 1 )-N(3) C(2)-N(1 )-Rh( 1 )-P( 1) N(2)-N(1)-Rh(1 )-P(1) C(4)-N(2)-B( I )-N(4) N(1 )-N(2)-B(1 )-N(4) C(4)-N(2)-B(1 )-N(6) N(1 )-N(2)-B(1 )-N(6) C(9)-N(4)-B( 1 )-N(2) N(3)-N(4)-B( 1 )-N(2) C(9)-N(4)-B( 1 )-N(6) N(3)-N(4)-B( 1 )-N(6)  88  Angle 174.44(11) 176.02(14) 1.37(18) -0.1(3) 2.0(3) -175.23(17) -85(2) -14(3) -168(2) 95(2) 45.16(17) -142.20(11) 126.27(17) 46.37(11) 139.12(17) -48.24(11) -131.1(6) 41.6(7) 53.6(4) -130.0(4) 125.56(16) -58.09(11) -152.55(16) 23.81(12) -54.75(16) 121.61(11) -39.85(18) 153.51(11) -134.16(18) 59.20(11) 144.10(17) -22.54(11) 49.46(17) -117.18(10) -116.39(18) 73.77(18) 125.50(17) -44.33(19) 123.19(19) -71.92(18) -117.19(19) 47.71(19) -  -  N(7)-C(3 6)-C(40)-C(39) C(3 5)-C(36)-C(40)-C(3 9) C(3>C(2)-N( 1 )-N(2) C( I )-C(2)-N( 1 )-N(2) C(3)-C(2)-N(1)-Rh(1) C(1 )-C(2)-N(1)-Rh(1) C(3)-C(4)-N(2)-N(1) C(5)-C(4)-N(2)-N(1) C(3)-C(4)-N(2)-B(1) C(5)-C(4)-N(2)-B(1) C(2)-N( 1 )-N(2)-C(4) Rh( 1 )-N( 1 )-N(2)-C(4) C(2)-N(1 )-N(2)-B(1) Rh(1 )-N(1)-N(2)-B(l) C(8)-C(7)-N(3)-N(4) C(6)-C(7)-N(3)-N(4) C(8)-C(7)-N(3)-Rh(1) C(6)-C(7)-N(3)-Rh(1) C(8)-C(9)-N(4)-N(3) C(1 0)-C(9)-N(4)-N(3) C(8)-C(9)-N(4)-B(1) C(1 0)-C(9)-N(4)-B(1) C(7)-N(3)-N(4)-C(9) Rh(1)-N(3)-N(4)-C(9) C(7)-N(3)-N(4)-B(1) Rh(1)-N(3)-N(4)-B(1) C( 1 3)-C( 1 2)-N(5)-N(6) C( 11 )-C( 1 2)-N(5)-N(6) C(1 3)-C(1 2)-N(5)-Rh(1) C( 11 )-C(1 2)-N(5)-Rh(1) C(1 3)-C( 1 4)-N(6)-N(5) C(1 5)-C(1 4)-N(6)-N(5) C(1 3)-C(14)-N(6)-B(1) C(1 5)-C(1 4)-N(6)-B(1) C(1 2)-N(5)-N(6)-C(1 4)  -2.4(3) 174.74(17) 2.05(18) 175.01(15) -165.22(13) 17.7(3) 1.72(19) -176.69(16) -168.91(16) 12.7(3) -2.35(18) 168.64(10) 169.24(14) -19.78(17) -2.15(19) 173.80(15) 174.50(13) -9.5(3) -1.4(2) 178.16(17) 164.43(17) -16.0(3) 2.20(18) -175.10(11) -165.56(14) 17.14(18) -0.13(18) -179.74(15) 172.94(12) -6.7(3) -0.22(19) 179.51(16) -175.65(16) 4.1(3) 0.21(18)  C( 1 4)-N(6)-B( 1 )-N(2) N(5)-N(6)-B( 1 )-N(2) C( 1 4)-N(6)-B( 1 )-N(4) N(5)-N(6)-B(1 )-N(4) C(2 1)-C(1 6)-P(1)-C(22) C(1 7)-C(1 6)-P(1)-C(22) C(2 1)-C(1 6)-P(1 )-C(28) C(1 7)-C(1 6)-P(1 )-C(28) C(2 1)-C(16)-P(1)-Rh(1) C(1 7)-C(1 6)-P(1 )-Rh(1) C(27)-C(22)-P( 1 )-C(1 6) C(23)-C(22)-P( 1 )-C(1 6) C(27)-C(22)-P(1)-C(28) C(23)-C(22)-P(1 )-C(28) C(27)-C(22)-P( 1 )-Rh( 1) C(23)-C(22)-P( 1 )-Rh( 1) C(29)-C(28)-P(1)-C(1 6) C(33)-C(28)-P(1)-C(1 6) C(29)-C(28)-P( 1 )-C(22) C(33)-C(28)-P(1 )-C(22) C(29)-C(28)-P(1 )-Rh(1) C(33)-C(28)-P(1 )-Rh(1) C(34)-Rh( 1 )-P( 1 )-C( 16) N(5)-Rh(1 )-P(1 )-C(1 6) N(3)-Rh(1 )-P(1 )-C(1 6) N(1)-Rh(1)-P(1)-C(1 6) C(34)-Rh( 1 )-P( 1 )-C(22) N(5)-Rh( 1 )-P( 1 )-C(22) N(3)-Rh(1 )-P(1 )-C(22) N(1 )-Rh( 1 )-P(1 )-C(22) C(34)-Rh( 1 )-P( 1 )-C(28) N(5)-Rh(1 )-P(1 )-C(28) N(3)-Rh(1)-P(1)-C(28) N(1 )-Rh(1 )-P(1 )-C(28) Rh(1)-N(5)-N(6)-C(1 4)  -  89  -126.28(17) 58.82(19) 114.30(18) -60.59(19) -1.79(17) -178.73(13) -104.65(15) 78.41(14) 126.86(14) -50.08(14) 116.69(16) -62.02(16) -137.38(15) 43.91(16) -5.93(17) 175.35(13) -10.51(16) 165.86(13) -118.13(14) 58.24(14) 111.04(13) -72.59(14) 167.32(7) -16.4(6) -21.20(7) 72.91(7) -72.26(8) 104.0(6) 99.22(7) -166.68(7) 49.01(8) -134.7(6) -139.51(7) -45.41(7) -174.44(11)  

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