Thioether-Directed NiH-Catalyzed Remote γ-C(sp3)-H Hydroamidation of Alkenes by 1,4,2-Dioxazol-5-ones

Bingnan Du; Yuxin Ouyang; Qishu Chen; Wing Yiu Yu

doi:10.1021/jacs.1c05834

Thioether-Directed NiH-Catalyzed Remote γ-C(sp³)-H Hydroamidation of Alkenes by 1,4,2-Dioxazol-5-ones

Bingnan Du, Yuxin Ouyang, Qishu Chen, Wing Yiu Yu

Research output: Journal article publication › Journal article › Academic research › peer-review

69 Citations (Scopus)

Abstract

A NiH-catalyzed thioether-directed cyclometalation strategy is developed to enable remote methylene C-H bond amidation of unactivated alkenes. Due to the preference for five-membered nickelacycle formation, the chain-walking isomerization initiated by the NiH insertion to an alkene can be terminated at the γ-methylene site remote from the alkene moiety. By employing 2,9-dibutyl-1,10-phenanthroline as the ligand and dioxazolones as the reagent, the amidation occurs at the γ-C(sp³)-H bonds to afford the amide products in up to 90% yield (>40 examples) with remarkable regioselectivity (up to 24:1 rr).

Original language	English
Pages (from-to)	14962-14968
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	143
Issue number	37
DOIs	https://doi.org/10.1021/jacs.1c05834
Publication status	Published - 22 Sept 2021

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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10.1021/jacs.1c05834

http://hdl.handle.net/10397/95735

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@article{89d685232d6245beaaf35981ff687e75,

title = "Thioether-Directed NiH-Catalyzed Remote γ-C(sp3)-H Hydroamidation of Alkenes by 1,4,2-Dioxazol-5-ones",

abstract = "A NiH-catalyzed thioether-directed cyclometalation strategy is developed to enable remote methylene C-H bond amidation of unactivated alkenes. Due to the preference for five-membered nickelacycle formation, the chain-walking isomerization initiated by the NiH insertion to an alkene can be terminated at the γ-methylene site remote from the alkene moiety. By employing 2,9-dibutyl-1,10-phenanthroline as the ligand and dioxazolones as the reagent, the amidation occurs at the γ-C(sp3)-H bonds to afford the amide products in up to 90% yield (>40 examples) with remarkable regioselectivity (up to 24:1 rr).",

author = "Bingnan Du and Yuxin Ouyang and Qishu Chen and Yu, {Wing Yiu}",

note = "Funding Information: We are grateful for financial support from the Hong Kong Research Grants Council (PolyU153152/16P, PolyU153023/17P, PolyU153017/19P) and the State Key Laboratory for Chemical Biology for Drug Discovery. We thank Prof. Xumu Zhang (Southern University of Science and Technology) for his support in this project. Publisher Copyright: {\textcopyright} 2021 American Chemical Society",

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language = "English",

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T1 - Thioether-Directed NiH-Catalyzed Remote γ-C(sp3)-H Hydroamidation of Alkenes by 1,4,2-Dioxazol-5-ones

AU - Du, Bingnan

AU - Ouyang, Yuxin

AU - Chen, Qishu

AU - Yu, Wing Yiu

N1 - Funding Information: We are grateful for financial support from the Hong Kong Research Grants Council (PolyU153152/16P, PolyU153023/17P, PolyU153017/19P) and the State Key Laboratory for Chemical Biology for Drug Discovery. We thank Prof. Xumu Zhang (Southern University of Science and Technology) for his support in this project. Publisher Copyright: © 2021 American Chemical Society

PY - 2021/9/22

Y1 - 2021/9/22

N2 - A NiH-catalyzed thioether-directed cyclometalation strategy is developed to enable remote methylene C-H bond amidation of unactivated alkenes. Due to the preference for five-membered nickelacycle formation, the chain-walking isomerization initiated by the NiH insertion to an alkene can be terminated at the γ-methylene site remote from the alkene moiety. By employing 2,9-dibutyl-1,10-phenanthroline as the ligand and dioxazolones as the reagent, the amidation occurs at the γ-C(sp3)-H bonds to afford the amide products in up to 90% yield (>40 examples) with remarkable regioselectivity (up to 24:1 rr).

AB - A NiH-catalyzed thioether-directed cyclometalation strategy is developed to enable remote methylene C-H bond amidation of unactivated alkenes. Due to the preference for five-membered nickelacycle formation, the chain-walking isomerization initiated by the NiH insertion to an alkene can be terminated at the γ-methylene site remote from the alkene moiety. By employing 2,9-dibutyl-1,10-phenanthroline as the ligand and dioxazolones as the reagent, the amidation occurs at the γ-C(sp3)-H bonds to afford the amide products in up to 90% yield (>40 examples) with remarkable regioselectivity (up to 24:1 rr).

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U2 - 10.1021/jacs.1c05834

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SN - 0002-7863

VL - 143

SP - 14962

EP - 14968

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 37

ER -

Thioether-Directed NiH-Catalyzed Remote γ-C(sp³)-H Hydroamidation of Alkenes by 1,4,2-Dioxazol-5-ones

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