Studies towards the total synthesis of labiatin A

QD Chemistry

Vignard, David ; Clark, J. Stephen

University:University of Glasgow

Department:School of Chemistry

关键词: labiatin A, natural product, total synthesis, diazo carbonyl compounds, metal carbenoid, C-H insertion, oxonium ylide, rearrangement.;   

Others  :  http://theses.gla.ac.uk/357/1/2008vignard1phd.pdf

来源: University of Glasgow

【 摘 要 】

This thesis is concerned with studies towards the total synthesis of labiatin A using metal carbenoid chemistry. The work described herein shows the most recent contribution to this field from our research group.Chapter I provides an introduction to metal carbenoids and their uses in organic synthesis. In particular, the synthesis of diazo carbonyl compounds, their decomposition by metal catalysts leading to the formation of metal carbenoids and the reactions involving metal carbenoids is described. A retrosynthesis of labiatin A involving the use of two metal-carbenoid transformations- intramolecular C-H insertion reaction and oxonium ylide formation followed by [2,3]-sigmatropic rearrangement- is presented.In Chapter II, the successful applications of these two reactions to the enantioselective synthesis of the tricyclic core of labiatin A is described. This is followed by the description of the different attempts to complete the synthesis of labiatin A. Finally, the exploration of a modified approach to the total synthesis of labiatin A is described.Chapter III provides the analytical support to this thesis.