From Ketones to Esters by a Cu-Catalyzed Highly Selective C(CO)-C(alkyl) Bond Cleavage: Aerobic Oxidation and Oxygenation with Air

被引：209

作者：

Huang, Xiaoqiang ^{[1
]}

Li, Xinyao ^{[1
]}

Zou, Miancheng ^{[1
]}

Song, Song ^{[1
]}

Tang, Conghui ^{[1
]}

Yuan, Yizhi ^{[1
]}

Jiao, Ning ^{[1
,2
]}

机构：

[1] Peking Univ, Sch Pharmaceut Sci, State Key Lab Nat & Biomimet Drugs, Beijing 100191, Peoples R China

[2] E China Normal Univ, Shanghai Key Lab Green Chem & Chem Proc, Shanghai 200062, Peoples R China

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2014年 / 136卷 / 42期

基金：

中国国家自然科学基金;

关键词：

CARBON-CARBON BOND; MOLECULAR-OXYGEN; DIOXYGEN ACTIVATION; ORGANIC-CHEMICALS; TERMINAL ALKYNES; METHYL KETONES; ARYL BROMIDES; HALLER-BAUER; PALLADIUM; ALDEHYDES;

D O I：

10.1021/ja5073004

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The Cu-catalyzed aerobic oxidative esterification of simple ketones via C-C bond cleavage has been developed. Varieties of common ketones, even inactive aryl long-chain alkyl ketones, are selectively converted into esters. The reaction tolerates a wide range of alcohols, including primary and secondary alcohols, chiral alcohols with retention of the configuration, electron-deficient phenols, as well as various natural alcohols. The usage of inexpensive copper catalyst, broad substrate scope, and neutral and open air conditions make this protocol very practical. O-18 labeling experiments reveal that oxygenation occurs during this transformation. Preliminary mechanism studies indicate that two novel pathways are mainly involved in this process.

引用

页码：14858 / 14865

页数：8

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