Rhodium(I)-Catalyzed Enantioselective Cyclization of Enynes through Site-Selective C(sp³)–H Bond Activation Triggered by Formation of Rhodacycle

Abstract

Rhodium(I)-catalyzed enantioselective cyclization of enynes through C(sp³)–H bond activation was investigated. It was found that the cyclization of enynes having a tert-butyl moiety on the alkene afforded a spirocyclic compound (up to 92% ee), while the cyclization of enynes having an isopropyl or an ethyl group on the alkene gave a cyclic diene (up to 98% ee). Furthermore, an intermolecular competition reaction using a deuterium-labeled substrate revealed that C(sp³)–H bond activation was one of the key steps, having a high energy barrier, in this cyclization.

Key words

rhodium - enantioselective cyclization - C(sp³)–H bond activation - alkene - alkyne - enyne

Publication History

Received: 11 March 2021

Accepted after revision: 30 March 2021

Accepted Manuscript online:
30 March 2021

Article published online:
22 April 2021

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