New approaches for the stereoselective synthesis of N-heterocycles

QD Chemistry

Daly, Mark ; Sutherland, Andrew

University:University of Glasgow

Department:School of Chemistry

关键词: organic, synthesis, stereoselective, heterocycle, overman, rearrangement, metathesis, cyclisation, pyrrolidones, piperidones, lactam, pipecolic, quaternary, claisen;   

Others  :  http://theses.gla.ac.uk/3807/1/2012dalyphd.pdf

来源: University of Glasgow

【 摘 要 】

A stereoselective approach has been developed for the flexible synthesis of substituted 2-pyrrolidones and 2-piperidones. By employing the key Overman rearrangement, efficient transfer of stereochemistry was achieved, and an acylation and ring closing metathesis strategy afforded a library of target N-heterocycles.In addition, the optimisation of a synthesis of 4-oxopipecolic acid derivatives from L-aspartic acid was investigated. A novel, milder and higher yielding 6-endo-trig cyclisation procedure was developed. This allowed for the generation of a library of 2,6-cis-substituted 4-oxopipecolic derivatives. Stereoselective carbonyl reduction extended the synthesis further to include 4-hydroxypipecolic acid derivatives.