Nickel-Catalyzed Reductive 4+1 Sila-Cycloaddition of 1,3-Dienes with Dichlorosilanes

摘要

Transition-metal-catalyzedsila-cycloaddition has been a promisingtool for accessing silacarbocycle derivatives, but the approach hasbeen limited to a selection of well-defined sila-synthons. Herein,we demonstrate the potential of chlorosilanes, which are industrialfeedstock chemicals, for this type of reaction under reductive nickelcatalysis. This work extends the scope of reductive coupling fromcarbocycle to silacarbocycle synthesis and from single C-Sibond formation to sila-cycloaddition reactions. The reaction proceedsunder mild conditions and shows good substrate scope and functionalitytolerance, and it offers new access to silacyclopent-3-enes and spirosilacarbocycles. The optical properties of several spiro dithienosilolesas well as structural variations of the products are demonstrated.