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

2014; American Chemical Society; Volume: 136; Issue: 42 Linguagem: Inglês

10.1021/ja5073004

1943-2984

Xiaoqiang Huang, Xinyao Li, Miancheng Zou, Song Song, Conghui Tang, Yizhi Yuan, Ning Jiao,

Synthesis and Catalytic Reactions

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. 18O labeling experiments reveal that oxygenation occurs during this transformation. Preliminary mechanism studies indicate that two novel pathways are mainly involved in this process.