Bai-Lin Wang, Hongliang Zhao, Xing-Wang Wang* and Senmiao Xu*,
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Merging Ring-Opening 1,2-Metallate Shift with Asymmetric C(sp3)–H Borylation of Aziridines
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(sp3)–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.
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