Rhodium(III)-Catalyzed Annulative Carbooxygenation of 1,1-Disubstituted Alkenes Triggered by C−H Activation

Yang Li; Yuhai Tang; Xin He; Dandan Shi; Jun Wu; Silong Xu

doi:10.1002/chem.201701703

Rhodium(III)-Catalyzed Annulative Carbooxygenation of 1,1-Disubstituted Alkenes Triggered by C−H Activation

Yang Li
, Yuhai Tang
, Xin He
, Dandan Shi
, Jun Wu
, Silong Xu

School of Chemistry

Xi'an Jiaotong University

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

22 Scopus citations

Abstract

A Cp*Rh^III-catalyzed annulative carbooxygenation of challenging 1,1-disubstituted alkenes triggered by C−H activation of N-aryloxyacetamides has been established, which affords 2,3-dihydrobenzofuran derivatives with a quaternary carbon center in good to excellent yields under mild redox-neutral conditions. An amide group on the alkenes is essential for the process, and may inhibit the β-H elimination from C(sp3)−Rh species by saturating the rhodium center through coordination. Furthermore, mechanistic insights obtained from control experiments suggest a mechanism involving a Rh^III-Rh^V-Rh^III catalytic cycle.

Original language	English
Pages (from-to)	7453-7457
Number of pages	5
Journal	Chemistry - A European Journal
Volume	23
Issue number	31
DOIs	https://doi.org/10.1002/chem.201701703
State	Published - 1 Jun 2017

Keywords

1,1-disubstituted alkenes
Cp*Rh catalysis
C−H activation
annulation
carbooxygenation

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10.1002/chem.201701703

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title = "Rhodium(III)-Catalyzed Annulative Carbooxygenation of 1,1-Disubstituted Alkenes Triggered by C−H Activation",

abstract = "A Cp*RhIII-catalyzed annulative carbooxygenation of challenging 1,1-disubstituted alkenes triggered by C−H activation of N-aryloxyacetamides has been established, which affords 2,3-dihydrobenzofuran derivatives with a quaternary carbon center in good to excellent yields under mild redox-neutral conditions. An amide group on the alkenes is essential for the process, and may inhibit the β-H elimination from C(sp3)−Rh species by saturating the rhodium center through coordination. Furthermore, mechanistic insights obtained from control experiments suggest a mechanism involving a RhIII-RhV-RhIII catalytic cycle.",

keywords = "1,1-disubstituted alkenes, Cp*Rh catalysis, C−H activation, annulation, carbooxygenation",

author = "Yang Li and Yuhai Tang and Xin He and Dandan Shi and Jun Wu and Silong Xu",

note = "Publisher Copyright: {\textcopyright} 2017 Wiley-VCH Verlag GmbH \& Co. KGaA, Weinheim",

year = "2017",

month = jun,

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doi = "10.1002/chem.201701703",

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T1 - Rhodium(III)-Catalyzed Annulative Carbooxygenation of 1,1-Disubstituted Alkenes Triggered by C−H Activation

AU - Li, Yang

AU - Tang, Yuhai

AU - He, Xin

AU - Shi, Dandan

AU - Wu, Jun

AU - Xu, Silong

PY - 2017/6/1

Y1 - 2017/6/1

N2 - A Cp*RhIII-catalyzed annulative carbooxygenation of challenging 1,1-disubstituted alkenes triggered by C−H activation of N-aryloxyacetamides has been established, which affords 2,3-dihydrobenzofuran derivatives with a quaternary carbon center in good to excellent yields under mild redox-neutral conditions. An amide group on the alkenes is essential for the process, and may inhibit the β-H elimination from C(sp3)−Rh species by saturating the rhodium center through coordination. Furthermore, mechanistic insights obtained from control experiments suggest a mechanism involving a RhIII-RhV-RhIII catalytic cycle.

AB - A Cp*RhIII-catalyzed annulative carbooxygenation of challenging 1,1-disubstituted alkenes triggered by C−H activation of N-aryloxyacetamides has been established, which affords 2,3-dihydrobenzofuran derivatives with a quaternary carbon center in good to excellent yields under mild redox-neutral conditions. An amide group on the alkenes is essential for the process, and may inhibit the β-H elimination from C(sp3)−Rh species by saturating the rhodium center through coordination. Furthermore, mechanistic insights obtained from control experiments suggest a mechanism involving a RhIII-RhV-RhIII catalytic cycle.

KW - 1,1-disubstituted alkenes

KW - CpRh catalysis

KW - C−H activation

KW - annulation

KW - carbooxygenation

UR - https://www.scopus.com/pages/publications/85019544179

U2 - 10.1002/chem.201701703

DO - 10.1002/chem.201701703

M3 - 文章

C2 - 28440028

AN - SCOPUS:85019544179

SN - 0947-6539

VL - 23

SP - 7453

EP - 7457

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 31

ER -

Rhodium(III)-Catalyzed Annulative Carbooxygenation of 1,1-Disubstituted Alkenes Triggered by C−H Activation

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Keywords

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