Ni-Catalyzed Decarboxylative Silylation of Alkynyl Carbonates: Access to Chiral Allenes via Enantiospecific Conversions

A Ni-mediated decarboxylative silylation of alkynyl cyclic carbonates used as versatile propargylic surrogates is reported affording a wide range of highly substituted 2,3- and 3,4-allenol products in good yields. The formal cross-coupling between a tentative intermediate Ni(allenyl) and the silyl reagent was further extended to enantiospecific conversions providing access to chiral allene synthons. This protocol marks the first Ni-catalyzed propargylic silylation proceeding through an S(N)2' manifold.

Automated summary

A Ni-catalyzed decarboxylative silylation of alkynyl cyclic carbonates has been reported, which serves as versatile propargylic surrogates and affords a wide range of highly substituted 2,3- and 3,4-allenol products in good yields. The formal cross-coupling between a tentative intermediate Ni(allenyl) and the silyl reagent can be further extended to enantiospecific conversions providing access to chiral allene synthons. This study is of significance as it represents the first Ni-catalyzed propargylic silylation proceeding through an S(N)2' manifold.