Copper(I) chloride-mediated intramolecular conjugate additions of vinyltrimethylstannane functions to [alpha],[beta]-alkynic esters
department or school: Science, Faculty of
department or school: Chemistry, Department of
data provider: DSpace
degree campus: UBCV
creator: Boehringer, Eva-Maria
issued: 2009-02-17T19:44:53Z
issued: 1996
related degree: Master of Science - MSc
degree grantor: University of British Columbia
description: In this thesis, the development of a method that effects copper(I) chloride-mediated intramolecular conjugate additions of vmyltrimethylstannane functions to a,|3-alkynic esters is described. The alJkenyltrimethylstannanes 21, 22 and 23 were prepared in a stereoselective fashion in moderate to good yields by the addition of hthium (trimethylstannyl)(cyano)cuprate (48) to the appropriate dialkyl dialkynedioates 42, 43 and 44. Syntheses of the alkenyltrimethylstannanes 31, 32, 33 and 37 were achieved by addition of methyl 3-lithiopropynoate (62) to the aldehydes 63, 66a, 66b and 70, respectively. These aldehydes were, in turn, prepared from the corresponding ß-trimethylstannyl a,ßy- or ßy-unsaturated esters (50, 68a, 68b, 72) via a sequence of standard transformations. The copper(I) chloride-mediated intramolecular conjugate additions of the alkenyltrimethylstannanes 21-23 and 31-33 were carried out successfully, thus demonstrating the viability of the proposed method. The general utility of the method was shown by the synthesis of several highly functionalized mono- and bicyclic ring systems (24-26, 34-36). A limitation of the method was shown by the failure of the attempted cyclization of the substituted alkenyltrimethylstannane 37. [Formula on pages 4 and 5 of Abstract]
aggregated CHO: https://circle.library.ubc.ca/rest/handle/2429/4692
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note: COPPER(I) CHLORIDE-MEDIATED INTRAMOLECULAR CONJUGATE ADDITIONS OF VINYLTRIMETHYLSTANNANE FUNCTIONS TO a ,P-ALKYNIC ESTERS by EVA-MARIA BOEHRINGER B. Sc., The University of Waterloo, 1994 A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE in THE FACULTY OF GRADUATE STUDIES (Department of Chemistry) We accept this thesis as conforming to the required standard THE UNIVERSITY OF BRITISH COLUMBIA August 1996 © Eva-Maria Boehringer, 1996 In presenting this thesis in partial fulfilment of the requirements for an advanced degree at the University of British Columbia, I agree that the Library shall make it freely available for reference and study. I further agree that permission for extensive copying of this thesis for scholarly purposes may be granted by the head of my department or by his or her representatives. It is understood that copying or publication of this thesis for financial gain shall not be allowed without my written permission. Department of Chun's' The University of British Columbia Vancouver, Canada Date %. 0<t.),{ DE-6 (2/88) 11 A B S T R A C T In this thesis, the development of a method that effects copper(I) chloride-mediated intramolecular conjugate additions of vmyltrimethylstannane functions to a,|3-alkynic esters is described. The alJkenyltrimethylstannanes 21, 22 and 23 were prepared in a stereoselective fashion in moderate to good yields by the addition of hthium (trimethylstannyl)(cyano)cuprate (48) to the appropriate dialkyl dialkynedioates 42, 43 and 44. Syntheses of the alkenyltrimethylstannanes 31, 32, 33 and 37 were achieved by addition of methyl 3-lithiopropynoate (62) to the aldehydes 63, 66a, 66b and 70, respectively. These aldehydes were, in turn, prepared from the corresponding P-trimethylstannyl a,(3- or (3,y-unsaturated esters (50, 68a, 68b, 72) via a sequence of standard transformations. The copper(I) chloride-mediated intramolecular conjugate additions of the alkenyl-trimethylstannanes 21…
has type: Thesis/Dissertation
date issued: 1996-11
is shown at: 10.14288/1.0061755
language: eng
degree discipline: Chemistry
provider: Vancouver : University of British Columbia Library
publisher: University of British Columbia
rights: For non-commercial purposes only, such as research, private study and education. Additional conditions apply, see Terms of Use https://open.library.ubc.ca/terms_of_use.
scholar level: Graduate
type: Text
identifier URI: http://hdl.handle.net/2429/4692