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Copper(I) chloride-mediated intramolecular conjugate additions of vinyltrimethylstannane functions to [alpha],[beta]-alkynic esters

University of British Columbia

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]

Thesis/Dissertation

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2009-02-17

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http://hdl.handle.net/2429/4692

Chemistry

University of British Columbia

UBCV

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