β‐Silylmethylene Malonate as Versatile Reagent in Organic Synthesis

Abstract

AbstractA silicon group plays distinctive role in controlling many organic reactions. In this context a β‐silylmethylene malonate (β‐SMM) can be considered as a versatile reagent in organic synthesis to introduce a silicon group in strategic positions of organic frameworks for further manipulations. In addition to the chemistry exhibited by alkylidene and arylidene malonates, a β‐SMM shows unique reaction attributed to the silicon group. The derived products exhibit enormous potential for the rapid generation of useful intermediates/products which are otherwise difficult to accomplish. This account chronicles our systematic approach beginning from the synthesis of β‐SMMs from readily available starting materials, and their use in complexity generation through novel and/ or known reactions. Reactions using β‐SMMs such as synthesis of 1‐substituted vinylsilanes and their Pd‐catalyzed cross‐coupling, organocatalytic asymmetric addition of methyl ketones, aldehydes, nitroalkanes and pyrazol‐5‐ones, and asymmetric 1,3‐dipolar cycloaddition with azomethine ylides are highly influenced by the silicon group.