Selectivity in Rh-catalysis with <i>gem</i>-difluorinated cyclopropanes

Zeng, Yaxin; Jiang, Zhong-Tao; Xia, Ying

doi:10.1039/d4cc00793j

Cited by 4 publications

(1 citation statement)

References 86 publications

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“…In recent years, gem -difluorinated cyclopropanes ( gem -DFCPs) have become a type of widely used substrates for the synthesis of monofluoro alkenes via ring-opening/cross-coupling reactions under transition-metal catalysis 30 – 36 . Our group has been devoted to the exploration of the reactivity of gem -DFCPs under rhodium catalysis 21 , 37 – 41 . These reactions involve a C–C bond activation and β-F elimination process, providing the key fluoroallyl-Rh intermediate marked by its heightened electrophilicity due to the electron-withdrawing effect of the fluorine and the cationic Rh.…”

Section: Introductionmentioning

confidence: 99%

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

Zeng,

Gao,

Jiang

et al. 2024

Nat Commun

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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.

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Section: Introductionmentioning

confidence: 99%

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

Zeng,

Gao,

Jiang

et al. 2024

Nat Commun

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Rhodium‐Catalyzed Enantio‐ and Regioselective Allylation of Indoles with gem‐Difluorinated Cyclopropanes

Yang,

Zeng,

Song

et al. 2024

Angewandte Chemie

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The use of gem‐difluorinated cyclopropanes (gem‐DFCPs) as fluoroallyl surrogates under transition‐metal catalysis has drawn considerable attention recently but such reactions are restricted to producing achiral or racemic mono‐fluoroalkenes. Herein, we report the first enantioselective allylation of indoles under rhodium catalysis with gem‐DFCPs. This reaction shows exceptional branched regioselectivity towards rhodium catalysis with gem‐DFCPs, which provides an efficient route to enantioenriched fluoroallylated indoles with wide substrate scope and good functional group tolerance.

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Rhodium‐Catalyzed Enantio‐ and Regioselective Allylation of Indoles with gem‐Difluorinated Cyclopropanes

Yang,

Zeng,

Song

et al. 2024

Angew Chem Int Ed

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Selectivity in Rh-catalysis with gem-difluorinated cyclopropanes

Abstract: The field of small-ring chemistry is fascinating in organic chemistry. gem-Difluorinated cyclopropanes, a unique class of cyclopropanes, have garnered significant interest due to their intrinsic high reactivity. In this context,...

Cited by 4 publications

References 86 publications

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

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

Rhodium‐Catalyzed Enantio‐ and Regioselective Allylation of Indoles with gem‐Difluorinated Cyclopropanes

Rhodium‐Catalyzed Enantio‐ and Regioselective Allylation of Indoles with gem‐Difluorinated Cyclopropanes

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