Advances in Exploring Heterocyclic Dienoxysilane Nucleophiles in Asymmetric Synthesis

The synthetic versatility of a special collection of heterocyclic dienoxysilane synthons based on furan, pyrrole, and thiophene to access valuable building blocks to be used in the fabrication of complex molecular architectures is featured. Accessed by base-assisted enolsilylation of alpha,beta-unsaturated lactone or lactam precursors, siloxydiene heterocycles easily couple in a strictly vinylogous sense to diverse electrophiles, such as aldol-, Mannich-, and Michael-type acceptors, to generate butenolide-type intermediates for viable use in asymmetric synthesis. A survey of our own achievements in this area, along with preeminent contributions by other research groups reveal the unique merits of siloxydiene chemistry and highlight these reactions as a key gateway to an array of multifunctional natural or natural-like constructs.