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Studies on asymmetric total synthesis of (-)-β-hydrastine via a chiral epoxide ring-opening cascade cyclization strategy.

ABSTRACT: Herein, facile and enantioselective approaches to synthesize the core phthalide tetrahydroisoquinoline scaffold of (-)-β-hydrastine via both a CF₃COOH-catalyzed (86% ee) and KHMDS-catalyzed (78% ee) epoxide ring-opening/transesterification cascade cyclization from chiral epoxide under very mild conditions are described. The key elements include a highly enantioselective epoxidation using the Shi ketone catalyst and an intramolecular CF₃COOH-catalyzed cascade cyclization in one pot, and a late-stage C-3' epimerization under MeOK/MeOH conditions as the key steps to achieve the first total synthesis of (-)-β-hydrastine (up to 81% ee).

SUBMITTER: Li J

PROVIDER: S-EPMC9053876 | biostudies-literature | 2020 May

REPOSITORIES: biostudies-literature

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Studies on asymmetric total synthesis of (-)-β-hydrastine via a chiral epoxide ring-opening cascade cyclization strategy.

Li Jihui J Wu Tianxiao T Song Xinjing X Zheng Yang Y Meng Jiaxin J Qin Qiaohua Q Liu Yongxiang Y Zhao Dongmei D Cheng Maosheng M

RSC advances 20200519 32

Herein, facile and enantioselective approaches to synthesize the core phthalide tetrahydroisoquinoline scaffold of (-)-β-hydrastine via both a CF3COOH-catalyzed (86% ee) and KHMDS-catalyzed (78% ee) epoxide ring-opening/transesterification cascade cyclization from chiral epoxide under very mild conditions are described. The key elements include a highly enantioselective epoxidation using the Shi ketone catalyst and an intramolecular CF3COOH-catalyzed cascade cyclizat ...[more]

PMID: 35518292

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