Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume -, Issue -, Pages -Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202306864
Keywords
Atropisomerism; Bridged Biaryls; Hydrolysis; Organocatalysis; Ring-Opening
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The development of catalytic asymmetric reactions using water as a reactant is challenging due to the low nucleophilicity and small size of water, which leads to reactivity and stereoselectivity control issues. In this study, we demonstrate a chiral phosphoric acid (CPA) catalyzed ring-opening reaction of biaryl oxazepines with water, achieving high enantioselectivity. The success of this reaction is attributed to the use of a new SPINOL-derived CPA catalyst and the high reactivity of biaryl oxazepine substrates towards water under acidic conditions. Density functional theory calculations suggest that the reaction proceeds via a dynamic kinetic resolution pathway, with the CPA catalyzed addition of water to the imine group being both enantio- and rate-determining.
The development of catalytic asymmetric reaction with water as the reactant is challenging due to the reactivity- and stereoselectivity-control issues resulted from the low nucleophilicity and the small size of water. We disclose herein a chiral phosphoric acid (CPA) catalyzed atroposelective ring-opening reaction of biaryl oxazepines with water. A series of biaryl oxazepines undergo the CPA catalyzed asymmetric hydrolysis in a highly enantioselective manner. The key for the success of this reaction is the use of a new SPINOL-derived CPA catalyst and the high reactivity of biaryl oxazepine substrates towards water under acidic conditions. Density functional theory calculations suggest that the reaction proceeds via a dynamic kinetic resolution pathway and the CPA catalyzed addition of water to the imine group is both enantio- and rate-determining.
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