Nickel-catalyzed [4 + 1] sila-cycloaddition: a divergent synthesis of silacarbocycles from trichlorosilanes

Abstract

Cyclic chlorosilane transformations present a valuable opportunity for the divergent synthesis of silacarbocycles, but their low availability has hindered this potential. This study presents a direct approach to producing structurally diverse five-membered cyclic chlorosilanes, utilizing trichlorosilanes as a novel Si-1 synthon for catalytic sila-cycloaddition reactions. The method employs a nickel-catalyzed [4 + 1] cycloaddition reaction between 1,3-dienes and trichlorosilanes, facilitated by upgraded phosphine–nitrogen ligands. This approach accommodates a broad range of 1,3-dienes and trichlorosilanes, yielding cyclic chlorosilanes that act as versatile platform molecules. These intermediates can be readily transformed into advanced silicon reagents and connected with various carbon and heteroatom functionalities through a one-pot reaction.