A General Strategy for the Asymmetric Preparation of α‐Stereogenic Allyl Silanes, Germanes, and Boronate Esters via Dual Copper Hydride‐ and Palladium‐Catalysis

Abstract

α‐Stereogenic allyl metalloids are versatile synthetic intermediates which can undergo various stereocontrolled transformations. Most existing methods to prepare α‐stereogenic allyl metalloids involve multi‐step sequences that curtail the number of compatible substrates and are limited to the synthesis of boronates. Here, we report a general method for the enantioselective preparation of α‐stereogenic allyl metalloids utilizing dual CuH‐ and Pd‐catalysis. This approach leverages a stereoretentive Cu‐to‐Pd transmetalation of an in situ generated alkyl copper species to allow access to enantioenriched allyl silanes, germanes, and boronate esters with broad functional group compatibility.

Catalytic Enantioselective Preparation of Chiral Allylsilanes

“…In 2022, Buchwald and co-workers [56] developed a general protocol for the access of the chiral α-stereogenic allyl metalloids, including the allylic silanes (Scheme 27). With (S)-DTBM-Segphos (L26), the asymmetric hydroalkenylation of vinyl metalloids could be achieved via the CuH and Pd relay catalysis, affording the silylated product 81 in good…”