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Catalytic Intramolecular Ketone Haloacylation Enabled Stereoselective Heterolytic Cleavage of Cyclopropyl Ketones with Enhanced Reactivity and Regioselectivity beyond Electronics
Organic Letters ( IF 5.2 ) Pub Date : 2024-05-08 , DOI: 10.1021/acs.orglett.4c01241
Siling Lei , Haoran Wang , Sunewang R. Wang

By integration of oxocarbenium activation and Lewis acid coordination activation via conformational proximity-driven, Pd(II)- or Cu(I)-catalyzed intramolecular ketone haloacylation, regio- and stereoselective heterolytic ring-opening 1,5-haloacylation of cyclopropyl ketones, including those with weak single alkyl donors, has been developed for the synthesis of valuable α-quaternary halo-γ-butenolides. The vicinal carboxylic acid and ketone acceptors are no longer just spectator activators. Further, this reaction delivers a constant regioselectivity regardless of the electronic nature of substituents, even the malonate.

中文翻译:

催化分子内酮卤酰化可实现环丙基酮的立体选择性杂解裂解,具有超越电子学的增强反应性和区域选择性

通过构象邻近驱动、Pd(II) 或 Cu(I) 催化的分子内酮卤酰化、环丙基酮的区域和立体选择性杂裂开环 1,5-卤酰化,将氧碳正离子活化和路易斯酸配位活化整合在一起,包括那些具有弱单烷基供体的化合物已被开发用于合成有价值的α-季卤代-γ-丁烯内酯。邻位羧酸和酮受体不再只是旁观激活剂。此外,无论取代基(甚至是丙二酸)的电子性质如何,该反应都提供恒定的区域选择性。
更新日期:2024-05-08
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