Nickel-Catalyzed anti-Markovnikov Hydroalkylation of Trifluoromethylalkenes

Chuan Zhu; Heng Zhang; Qian Liu; Kai Chen; Ze Yao Liu; Chao Feng

doi:10.1021/acscatal.2c02052

Nickel-Catalyzed anti-Markovnikov Hydroalkylation of Trifluoromethylalkenes

Chuan Zhu, Heng Zhang, Qian Liu, Kai Chen, Ze Yao Liu, Chao Feng

School of Chemistry and Moleculai Engineering

Nanjing Tech University

Research output: Contribution to journal › Article › peer-review

42 Scopus citations

Abstract

Transition-metal-catalyzed difunctionalization of olefins constitutes a fertile synthetic platform for rapid access to complex molecules from bulk chemicals. However, substrates featuring fluoroalkyl substituents are rarely employed because of facile β-fluoride elimination pathways. Herein, we report a hydroalkylation of trifluoromethylalkenes with alkyl halides under nickel catalysis that enables the rapid construction of 1,1,1-trifluoropropane derivatives. The common β-fluoride elimination pathway is suppressed by identifying a competent proton donor that favors a protonolysis process. Also, unactivated alkenes could be readily employed as the alkyl donor when using a Ni/hydrosilane catalytic system.

Original language	English
Pages (from-to)	9410-9417
Number of pages	8
Journal	ACS Catalysis
Volume	12
Issue number	15
DOIs	https://doi.org/10.1021/acscatal.2c02052
State	Published - 5 Aug 2022

Keywords

Ni-catalysis
anti-Markovnikov
hydroalkylation
inhibition of β-F elimination
protonolysis

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10.1021/acscatal.2c02052

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abstract = "Transition-metal-catalyzed difunctionalization of olefins constitutes a fertile synthetic platform for rapid access to complex molecules from bulk chemicals. However, substrates featuring fluoroalkyl substituents are rarely employed because of facile β-fluoride elimination pathways. Herein, we report a hydroalkylation of trifluoromethylalkenes with alkyl halides under nickel catalysis that enables the rapid construction of 1,1,1-trifluoropropane derivatives. The common β-fluoride elimination pathway is suppressed by identifying a competent proton donor that favors a protonolysis process. Also, unactivated alkenes could be readily employed as the alkyl donor when using a Ni/hydrosilane catalytic system.",

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author = "Chuan Zhu and Heng Zhang and Qian Liu and Kai Chen and Liu, {Ze Yao} and Chao Feng",

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T1 - Nickel-Catalyzed anti-Markovnikov Hydroalkylation of Trifluoromethylalkenes

AU - Zhu, Chuan

AU - Zhang, Heng

AU - Liu, Qian

AU - Chen, Kai

AU - Liu, Ze Yao

AU - Feng, Chao

PY - 2022/8/5

Y1 - 2022/8/5

N2 - Transition-metal-catalyzed difunctionalization of olefins constitutes a fertile synthetic platform for rapid access to complex molecules from bulk chemicals. However, substrates featuring fluoroalkyl substituents are rarely employed because of facile β-fluoride elimination pathways. Herein, we report a hydroalkylation of trifluoromethylalkenes with alkyl halides under nickel catalysis that enables the rapid construction of 1,1,1-trifluoropropane derivatives. The common β-fluoride elimination pathway is suppressed by identifying a competent proton donor that favors a protonolysis process. Also, unactivated alkenes could be readily employed as the alkyl donor when using a Ni/hydrosilane catalytic system.

AB - Transition-metal-catalyzed difunctionalization of olefins constitutes a fertile synthetic platform for rapid access to complex molecules from bulk chemicals. However, substrates featuring fluoroalkyl substituents are rarely employed because of facile β-fluoride elimination pathways. Herein, we report a hydroalkylation of trifluoromethylalkenes with alkyl halides under nickel catalysis that enables the rapid construction of 1,1,1-trifluoropropane derivatives. The common β-fluoride elimination pathway is suppressed by identifying a competent proton donor that favors a protonolysis process. Also, unactivated alkenes could be readily employed as the alkyl donor when using a Ni/hydrosilane catalytic system.

KW - Ni-catalysis

KW - anti-Markovnikov

KW - hydroalkylation

KW - inhibition of β-F elimination

KW - protonolysis

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DO - 10.1021/acscatal.2c02052

M3 - 文章

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Nickel-Catalyzed anti-Markovnikov Hydroalkylation of Trifluoromethylalkenes

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Keywords

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