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A Two-Step Protocol for Umpolung Functionalization of Ketones Via Enolonium Species
Published on: August 16, 2018
Intramolecular One-Carbon Homologation of Unstrained Ketones via C-C Activation-Enabled 1,1-Insertion of Alkenes
Jiangkun Huang1, Rui Zhang2, Xiuli Wu1
1West China School of Public Health and West China Fourth Hospital, and State Key Laboratory of Biotherapy, Sichuan University, Chengdu 610041, China.
Abstract:
Here, we describe the development of a Rh-catalyzed intramolecular one-carbon homologation of unstrained aryl ketones through a formal 1,1-insertion process of olefins, enabled by temporary directing group (TDG)-aided C-C activation. The reaction provides a distinct approach to access various substituted 1-indanones. Computational mechanistic studies reveal that the formal 1,1-insertion is realized by a selective C(sp2)-C(sp3) activation and turnover limiting 2,1-insertion into the alkene, followed by a facile β-H elimination and reinsertion process.
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