Observation of unusual outer-sphere mechanism using simple alkenes as nucleophiles in allylation chemistry

Yaxin Zeng, Han Gao, Zhong-Tao Jiang, Yulei Zhu, Jinqi Chen, Han Zhang, Gang Lu () and Ying Xia ()
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Yaxin Zeng: Sichuan University
Han Gao: Shandong University
Zhong-Tao Jiang: Sichuan University
Yulei Zhu: Sichuan University
Jinqi Chen: Sichuan University
Han Zhang: Sichuan University
Gang Lu: Shandong University
Ying Xia: Sichuan University

Nature Communications, 2024, vol. 15, issue 1, 1-10

Abstract: Abstract Transition-metal catalyzed allylic substitution reactions of alkenes are among the most efficient methods for synthesizing diene compounds, driven by the inherent preference for an inner-sphere mechanism. Here, we present a demonstration of an outer-sphere mechanism in Rh-catalyzed allylic substitution reaction of simple alkenes using gem-difluorinated cyclopropanes as allyl surrogates. This unconventional mechanism offers an opportunity for the fluorine recycling of gem-difluorinated cyclopropanes via C − F bond cleavage/reformation, ultimately delivering allylic carbofluorination products. The developed method tolerates a wide range of simple alkenes, providing access to secondary, tertiary fluorides and gem-difluorides with 100% atom economy. DFT calculations reveal that the C − C bond formation goes through an unusual outer-sphere nucleophilic substitution of the alkenes to the allyl-Rh species instead of migration insertion, and the generated carbon cation then forms the C − F bond with tetrafluoroborate as a fluoride shuttle.

Date: 2024
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DOI: 10.1038/s41467-024-48541-5

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