التفاصيل البيبلوغرافية
| العنوان: |
Observation of unusual outer-sphere mechanism using simple alkenes as nucleophiles in allylation chemistry. |
| المؤلفون: |
Zeng, Yaxin, Gao, Han, Jiang, Zhong-Tao, Zhu, Yulei, Chen, Jinqi, Zhang, Han, Lu, Gang, Xia, Ying |
| المصدر: |
Nature Communications; 5/21/2024, Vol. 15 Issue 1, p1-10, 10p |
| مصطلحات موضوعية: |
ALLYLATION, ALKENES, SUBSTITUTION reactions, NUCLEOPHILES, SCISSION (Chemistry), MUNICIPAL bonds |
| مستخلص: |
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. Allylic substitution reaction of alkenes has been well-developed, but it has limitations, partly due to the intrinsic predilection for an inner-sphere mechanism. Herein, the authors present an outer-sphere mechanism in Rh-catalyzed allylic substitution reaction of simple alkenes using gem-difluorinated cyclopropanes as allyl surrogates. [ABSTRACT FROM AUTHOR] |
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| قاعدة البيانات: |
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