Directing-Group-Free Arene C(sp2)-H Amination Using Bulky Aminium Radicals and DFT Analysis of Regioselectivity

被引：6

作者：

Behnke, Nicole Erin ^{[1
,2
]}

Kwon, Young-Do ^{[1
]}

Davenport, Michael T. ^{[3
]}

Ess, Daniel H. ^{[3
]}

Kurti, Laszlo ^{[1
]}

机构：

[1] Rice Univ, Dept Chem, Houston, TX 77030 USA

[2] Janssen Res & Dev, San Diego, CA 92121 USA

[3] Brigham Young Univ, Dept Chem & Biochem, Provo, UT 84602 USA

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2023年 / 88卷 / 16期

基金：

美国国家科学基金会; 美国国家卫生研究院;

关键词：

C-H AMINATION; CATALYZED AMINATION; ARYL HALIDES; ETHERS; ARYLAMINES; REDUCTION; AMINES; NITRO; ACIDS;

D O I：

10.1021/acs.joc.3c01127

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A hydroxylamine-derived electrophilicaminating reagentproducesa transient and bulky aminium radical intermediate upon insitu activation by either TMSOTf or TFA and a subsequentelectron transfer from an iron(II) catalyst. Density functional theorycalculations were used to examine the regioselectivity of arene C-Hamination reactions on diversely substituted arenes. The calculationssuggest a simple charge-controlled regioselectivity model that enablesprediction of the major C(sp(2))-H amination product.

引用

页码：11847 / 11854

页数：8

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