Selective C–F Bond Allylation of Trifluoromethylalkenes

Chuan Zhu; Meng Meng Sun; Kai Chen; Haidong Liu; Chao Feng

doi:10.1002/anie.202106531

Selective C–F Bond Allylation of Trifluoromethylalkenes

Chuan Zhu, Meng Meng Sun, Kai Chen, Haidong Liu, Chao Feng

School of Chemistry and Moleculai Engineering

Nanjing Tech University

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

60 Scopus citations

Abstract

Selective C−F bond functionalization of CF₃ group represents an appealing strategy for the incorporation of pharmaceutically privileged difluoromethylene moiety. Despite the recent significant advancement attained in the functionalization of Ar-CF₃ molecules, prescriptions amenable for alkenyl-CF₃ congeners remain sufficiently inadequate. Herein, we report a strategically novel protocol for the C−F bond elaboration of trifluoromethylalkene derivatives. By using readily available allyl metallics as nucleophilic coupling partner, the present reaction enables an expedient construction of structurally diversified CF₂-bridged 1,5-dienes. Furthermore, the exquisite selectivity observed in this transformation is revealed to be based on the underlying mechanism that consists of a cascade of nucleophilic S_N2′ defluorinative allylation and electronically promoted Cope rearrangement.

Original language	English
Pages (from-to)	20237-20242
Number of pages	6
Journal	Angewandte Chemie - International Edition
Volume	60
Issue number	37
DOIs	https://doi.org/10.1002/anie.202106531
State	Published - 6 Sep 2021

Keywords

CF-bridged 1,5-diene
Cope rearrangement
allylation
selective C−F bond functionalization
trifluoromethylalkene

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10.1002/anie.202106531

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title = "Selective C–F Bond Allylation of Trifluoromethylalkenes",

abstract = "Selective C−F bond functionalization of CF3 group represents an appealing strategy for the incorporation of pharmaceutically privileged difluoromethylene moiety. Despite the recent significant advancement attained in the functionalization of Ar-CF3 molecules, prescriptions amenable for alkenyl-CF3 congeners remain sufficiently inadequate. Herein, we report a strategically novel protocol for the C−F bond elaboration of trifluoromethylalkene derivatives. By using readily available allyl metallics as nucleophilic coupling partner, the present reaction enables an expedient construction of structurally diversified CF2-bridged 1,5-dienes. Furthermore, the exquisite selectivity observed in this transformation is revealed to be based on the underlying mechanism that consists of a cascade of nucleophilic SN2′ defluorinative allylation and electronically promoted Cope rearrangement.",

keywords = "CF-bridged 1,5-diene, Cope rearrangement, allylation, selective C−F bond functionalization, trifluoromethylalkene",

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T1 - Selective C–F Bond Allylation of Trifluoromethylalkenes

AU - Zhu, Chuan

AU - Sun, Meng Meng

AU - Chen, Kai

AU - Liu, Haidong

AU - Feng, Chao

PY - 2021/9/6

Y1 - 2021/9/6

N2 - Selective C−F bond functionalization of CF3 group represents an appealing strategy for the incorporation of pharmaceutically privileged difluoromethylene moiety. Despite the recent significant advancement attained in the functionalization of Ar-CF3 molecules, prescriptions amenable for alkenyl-CF3 congeners remain sufficiently inadequate. Herein, we report a strategically novel protocol for the C−F bond elaboration of trifluoromethylalkene derivatives. By using readily available allyl metallics as nucleophilic coupling partner, the present reaction enables an expedient construction of structurally diversified CF2-bridged 1,5-dienes. Furthermore, the exquisite selectivity observed in this transformation is revealed to be based on the underlying mechanism that consists of a cascade of nucleophilic SN2′ defluorinative allylation and electronically promoted Cope rearrangement.

AB - Selective C−F bond functionalization of CF3 group represents an appealing strategy for the incorporation of pharmaceutically privileged difluoromethylene moiety. Despite the recent significant advancement attained in the functionalization of Ar-CF3 molecules, prescriptions amenable for alkenyl-CF3 congeners remain sufficiently inadequate. Herein, we report a strategically novel protocol for the C−F bond elaboration of trifluoromethylalkene derivatives. By using readily available allyl metallics as nucleophilic coupling partner, the present reaction enables an expedient construction of structurally diversified CF2-bridged 1,5-dienes. Furthermore, the exquisite selectivity observed in this transformation is revealed to be based on the underlying mechanism that consists of a cascade of nucleophilic SN2′ defluorinative allylation and electronically promoted Cope rearrangement.

KW - CF-bridged 1,5-diene

KW - Cope rearrangement

KW - allylation

KW - selective C−F bond functionalization

KW - trifluoromethylalkene

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U2 - 10.1002/anie.202106531

DO - 10.1002/anie.202106531

M3 - 文章

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AN - SCOPUS:85111400115

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JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

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ER -

Selective C–F Bond Allylation of Trifluoromethylalkenes

Abstract

Keywords

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