Phosphine‐Catalyzed Activation of Vinylcyclopropanes: Rearrangement of Vinylcyclopropylketones to Cycloheptenones.
- Resource Type
- Article
- Authors
- Wu, Jun; Tang, Yuhai; Wei, Wen; Wu, Yong; Li, Yang; Zhang, Junjie; Zheng, Yuansuo; Xu, Silong
- Source
- Angewandte Chemie International Edition. 5/22/2018, Vol. 57 Issue 21, p6284-6288. 5p.
- Subject
- *PHOSPHINE
*ACTIVATION (Chemistry)
*VINYLCYCLOPROPANES
*REARRANGEMENTS (Chemistry)
*REACTION mechanisms (Chemistry)
*CHEMICAL yield
- Language
- ISSN
- 1433-7851
Abstract: We report a phosphine‐catalyzed activation of electron‐deficient vinylcyclopropanes (VCPs) to generate an ambident C5 synthon that is poised to undergo consecutive reactions. The utility of the activation is demonstrated in a phosphine‐catalyzed rearrangement of vinylcyclopropylketones to cycloheptenones in good yields with a broad substrate scope. Mechanistic investigations support a stepwise process comprising homoconjugate addition, water‐assisted proton transfer, and 7‐endo‐trig SN2′ ring closure. [ABSTRACT FROM AUTHOR]