A Pd-catalysed Decarboxylative Route to Functionalized Nitrogen Heterocycles

This thesis describes the synthesis of a pool of 5- and 6-membered sp3-rich N-heterocyclic compounds bearing orthogonal functionality via a Pd-catalysed decarboxylative allylation strategy.

An easily prepared trimethylene carbamate bearing different substituents at nitrogen reacted with Pd-catalysts for the in situ generation of a 1,4-dipole reagent that can react with α -fluoro-β-keto esters and sulfonium ylides to provide piperidines and pyrrolidines after cyclization.

The use of chiral catalysts or chiral auxiliaries provided a platform to access enantiomerically enriched products. In addition, we successfully employed stereochemical models in order to explain the stereochemical outcome in each case.

The potential of their downstream functionalization was fully showcased, and synthetic value was also proved by gram-scale reactions.