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Synthesis, polymerization and reactions of enantiomerically pure phosphaalkenes

University of British Columbia

This thesis outlines the polymerization and novel reactivity of enantiomerically pure compounds featuring the relatively uncommon phosphaalkene moiety. Chapter 1 introduces the chemistry of the phosphaalkene (Ar-P=CR₂) structural fragment. This motif is compared and contrasted to the established chemistry of C=N and C=C groups. Similarities and differences are highlighted by an examination of: (a) phosphaalkene synthesis, (b) phosphaalkene polymerization and (c) phosphaalkene-metal coordination. Chapter 2 details the addition reactions of MeM (M = MgBr, Li) nucleophiles to enantiomerically pure phosphaalkene-oxazoline 1.10a [PhAk-Ox, MesP=CPh(CMe₂Ox)]. Of note, the reaction of MeMgBr and PhAk-Ox is highly diastereoselective and affords a new P-chiral phosphine oxazoline ligand. Chapters 3 and 4 report the free radical initiated homo- and co-polymerizations (with styrene) of enantiomerically pure phosphaalkene-oxazolines 1.10a (Chapter 3) and 4.1a [MesP=CPh(3-C₆H₄Ox), Chapter 4]. The coordination of rhodium(I) to copolymers of 1.10a and styrene permits the isolation of novel macromolecular complexes. Additionally, polymers of 4.1a display unique spectroscopic signatures that permit the direct assignment of styrene-phosphaalkene linkages in the polymer backbone. Chapters 5 and 6 highlight the coordination chemistry of phosphaalkenes. Chapter 5 discusses the syntheses of κ³(PNN)-copper(I) complexes featuring enantiomerically pure pyridine-bridged phosphaalkene-oxazoline 5.1a [ArP=CPh(2-C₅H₃N-6-Ox)]. Chapter 6 explores the insertion of the P=C functional group into Pd–R bonds, permitting the synthesis of novel phosphapalladacyclopropanes (6.1a-b) and palladium(II) complexes featuring 1,2-dihydropyridinato donors (6.3 and 6.4). Chapter 7 provides perspective for the work contained within this thesis.

Text

2017-02-28

Attribution-NoDerivatives 4.0 International

http://hdl.handle.net/2429/58902

Chemistry

University of British Columbia

UBCV

http://creativecommons.org/licenses/by-nd/4.0/