Aerobic, Transition-Metal-Free, Direct, and Regiospecific Mono-α-arylation of Ketones: Synthesis and Mechanism by DFT Calculations

被引：89

作者：

Xu, Qing-Long ^{[1
]}

Gao, Hongyin ^{[1
]}

Yousufuddin, Muhammed ^{[2
]}

Ess, Daniel H. ^{[3
]}

Kuerti, Laszlo ^{[1
]}

机构：

[1] UT Southwestern Med Ctr, Dept Biochem, Div Chem, Dallas, TX 75390 USA

[2] Univ Texas Arlington, Ctr Nanostruct Mat, Arlington, TX 76019 USA

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

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2013年 / 135卷 / 38期

关键词：

SILYL ENOL ETHERS; OXIDATIVE NUCLEOPHILIC-SUBSTITUTION; DENSITY FUNCTIONALS; FACILE SYNTHESIS; METHYL KETONES; HYDROGEN; NITROARENES; ALDEHYDES; NITRILES; REAGENTS;

D O I：

10.1021/ja4074563

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We disclose a facile, aerobic, transitionmetal-free, direct, and regiospecific mono-alpha-arylation of ketones to yield aryl benzyl and (cyclo)alkyl benzyl ketones with substitution patterns that are currently inaccessible or challenging to prepare using conventional methods. The transformation is operationally simple, scalable, and environmentally friendly. There is no need for pre-functionalization (i.e., alpha-halogenation or silyl enol ether formation) or the use of specialized arylating agents (i.e., diaryliodonium salts). DFT calculations suggest that the in situ-generated enolate undergoes direct C-C bond formation with the nitroarene followed by regioselective O-2-mediated C-H oxidation.

引用

页码：14048 / 14051

页数：4

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