Merging Ring-Opening 1,2-Metallate Shift with Asymmetric C(<i>sp</i>³)–H Borylation of Aziridines

Abstract

Chiral secondary alkyl amines with a vicinal quaternary stereocenter are undoubtedly important and ubiquitous subunits in natural products and pharmaceuticals. However, their asymmetric synthesis remains a formidable challenge. Herein, we merge the ring-opening 1,2-metallate shift with iridium-catalyzed enantioselective C( sp 3 )–H borylation of aziridines to deliver these frameworks with high enantioselectivities. We also demonstrated the synthetic application by downstream transformations, including the total synthesis of two Amaryllidaceae alkaloids, (−)-crinane and (+)-mesmebrane.

Topics & Concepts