Development of Novel Transition Metal Catalyzed Transformations Involving Small, Strained Carbocycles

Abstract

This document deals with 3-membered carbocycles; their use as ligands for the asymmetric Heck reaction (AHR), the development of novel methods for their synthesis, and reactions for their further functionalization. The first chapter discusses a novel class of cyclopropyl containing phosphanyl-oxazoline (PHOX) ligands which were developed for the palladium catalyzed AHR coupling of aryl-triflates with furans. The following chapter addresses the development of a high-throughput method for the asymmetric hydroformylation of styrenes. The final chapter discusses two methods for the synthesis of cyclopropenes, one of which involves the using of 18-crown-6 for facilitation of the dehydrobromination of cyclopropyl monobromides. The cyclopropenes obtained via these methods were then used in the development of an asymmetric, rhodium catalyzed hydroformylation process which resulted in the formation of chiral, non-racemic cyclopropylcarboxaldehydes in reasonable yield and ee.