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Cobalt-Catalyzed Asymmetric Sequential Hydroboration/Isomerization/Hydroboration of 2-Aryl Vinylcyclopropanes
Chenhui Chen1, Hongliang Wang1,2, Tongtong Li1
1Department of Chemistry, Zhejiang University, Hangzhou, 310058, China.
Abstract:
A cobalt-catalyzed asymmetric sequential hydroboration/isomerization/hydroboration of 2-aryl vinylcyclopropanes was for the first time reported for the preparation of valuable chiral 1,5-bis(boronates) in good yields with excellent enantioselectivity via asymmetric sequential isomerization/hydroboration of a trisubstituted alkene intermediate. The reaction was carried out smoothly and this protocol was used for asymmetric syntheses of (-)-preclamol in gram-scale. The two primary C(sp3) -B bonds in chiral 1,5-bis(boronates) could be distinguished in iterative Suzuki-Miyaura cross-coupling reaction, delivering chiral 1,2,5-triaryl alkanes with excellent enantioselectivity. Based on experimental and computational studies, a cobalt-hydride species was proposed as the active intermediate in hydroboration, isomerization, and second hydroboration reactions.
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