Remote Allylation of Unactivated C(sp3)-H Bonds Triggered by Photogenerated Amidyl Radicals

Bin Xu; Uttam K. Tambar

doi:10.1021/acscatal.9b00563

Remote Allylation of Unactivated C(sp³)-H Bonds Triggered by Photogenerated Amidyl Radicals

Bin Xu, Uttam K. Tambar

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

47 Scopus citations

Abstract

The allylation reaction is a highly versatile transformation in chemical synthesis. While many elegant direct C(sp²)-H allylation reactions have been developed, the direct allylation of unactivated C(sp³)-H bonds is underdeveloped. By applying photoredox catalysis and a [1,5]-HAT process, herein we report a direct allylation of unactivated C(sp³)-H bonds. This photocatalyzed transformation is tolerant of several functional groups in the amide and allylic chloride substrates. Various allyl-substituted amide products were obtained with good yields and high δ-selectivity.

Original language	English (US)
Pages (from-to)	4627-4631
Number of pages	5
Journal	ACS Catalysis
Volume	9
Issue number	5
DOIs	https://doi.org/10.1021/acscatal.9b00563
State	Published - May 3 2019

Keywords

C(sp)-H
[1,5]-HAT
allylation
photocatalysis
radical
δ-selectivity

ASJC Scopus subject areas

Catalysis
Chemistry(all)

Access to Document

10.1021/acscatal.9b00563

Cite this

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title = "Remote Allylation of Unactivated C(sp3)-H Bonds Triggered by Photogenerated Amidyl Radicals",

abstract = "The allylation reaction is a highly versatile transformation in chemical synthesis. While many elegant direct C(sp2)-H allylation reactions have been developed, the direct allylation of unactivated C(sp3)-H bonds is underdeveloped. By applying photoredox catalysis and a [1,5]-HAT process, herein we report a direct allylation of unactivated C(sp3)-H bonds. This photocatalyzed transformation is tolerant of several functional groups in the amide and allylic chloride substrates. Various allyl-substituted amide products were obtained with good yields and high δ-selectivity.",

keywords = "C(sp)-H, [1,5]-HAT, allylation, photocatalysis, radical, δ-selectivity",

author = "Bin Xu and Tambar, {Uttam K.}",

note = "Funding Information: Financial support was provided by W. W. Caruth, Jr. Endowed Scholarship, Welch Foundation (I-1748), National Institutes of Health (R01GM102604), American Chemical Society Petroleum Research Fund (59177-ND1), Teva Pharmaceuticals Marc A. Goshko Memorial Grant (60011-TEV), and Sloan Research Fellowship. We acknowledge Ludovic Troian-Gautier (UNC) and Tian Qin (UTSW) for fruitful discussions. Publisher Copyright: {\textcopyright} 2019 American Chemical Society.",

year = "2019",

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doi = "10.1021/acscatal.9b00563",

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AU - Xu, Bin

AU - Tambar, Uttam K.

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PY - 2019/5/3

Y1 - 2019/5/3

N2 - The allylation reaction is a highly versatile transformation in chemical synthesis. While many elegant direct C(sp2)-H allylation reactions have been developed, the direct allylation of unactivated C(sp3)-H bonds is underdeveloped. By applying photoredox catalysis and a [1,5]-HAT process, herein we report a direct allylation of unactivated C(sp3)-H bonds. This photocatalyzed transformation is tolerant of several functional groups in the amide and allylic chloride substrates. Various allyl-substituted amide products were obtained with good yields and high δ-selectivity.

AB - The allylation reaction is a highly versatile transformation in chemical synthesis. While many elegant direct C(sp2)-H allylation reactions have been developed, the direct allylation of unactivated C(sp3)-H bonds is underdeveloped. By applying photoredox catalysis and a [1,5]-HAT process, herein we report a direct allylation of unactivated C(sp3)-H bonds. This photocatalyzed transformation is tolerant of several functional groups in the amide and allylic chloride substrates. Various allyl-substituted amide products were obtained with good yields and high δ-selectivity.

KW - C(sp)-H

KW - [1,5]-HAT

KW - allylation

KW - photocatalysis

KW - radical

KW - δ-selectivity

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