Enantio‐ and Regioselective Cascade Hydroboration of Methylenecyclopropanes for Facile Access to Chiral 1,3‐ and 1,4‐Bis(boronates)

Abstract

Abstract Chiral 1, n‐bis(boronate) plays a crucial role in organic synthesis and medicinal chemistry. However, their catalytic and asymmetric synthesis has long posed a challenge in terms of operability and accessibility from readily available substrates. The recent discovery of the C═C bond formation through β‐C elimination of methylenecyclopropanes (MCP) has provided an exciting opportunity to enhance molecular complexity. In this study, the catalyzed asymmetric cascade hydroboration of MCP is developed. By employing different ligands, various homoallylic boronate intermediate are obtained through the hydroboration ring opening process. Subsequently, the cascade hydroboration with HBpin or B2pin2 resulted in the synthesis of enantioenriched chiral 1,3‐ and 1,4‐bis(boronates) in high yields, accompanied by excellent chemo‐ and enantioselectivities. The selective transformation of these two distinct C─B bonds also demonstrated their application potential in organic synthesis.

Keywords

• bis(boronates)
• cascade reaction
• C─C bond cleavage
• hydroboration