Rhodium-Stabilized Vinylcarbenoid Intermediates in Organic Synthesis

Abstract

Abstract: This article will give an overview of the reactions and synthetic utility of rhodium-stabilized vinylcarbenoids, which have been shown in recent years to be versatile synthetic intermediates. They undergo highly diastereoselective cyclopropanations with a wide array of alkenes and dienes, and the resulting vinylcyclopropanes are readily converted to other ring systems. Most notable is the reaction between vinylcarbenoids and dienes, which is a general method for the stereoselective construction of seven-membered carbocycles by means of a tandem cyclopropanation/Cope rearrangement sequence. Efficient insertions into Si-H, C-H, N-H and 0-H bonds can also be achieved by rhodium-stabilized vinylcarbenoids. The synthetic utility of vinylcarbenoid chemistry has been greatly enhanced by the recent development of chiral catalysts and auxiliaries that enable this chemistry to be achieved with high asymmetric induction.