Cobalt-catalyzed direct transformation of aldehydes to esters: The crucial role of an enone as a mediator

Biao Lin Jiang; Yang Lin; Meng Liang Wang; Dian Sheng Liu; Bao Hua Xu; Suo Jiang Zhang

doi:10.1039/c8qo01298a

Cobalt-catalyzed direct transformation of aldehydes to esters: The crucial role of an enone as a mediator

Biao Lin Jiang, Yang Lin, Meng Liang Wang, Dian Sheng Liu^*, Bao Hua Xu, Suo Jiang Zhang

^*Corresponding author for this work

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

10 Citations (Scopus)

Abstract

An oxidative esterification of aldehydes with alkanols catalyzed by an in situ generated low-valent cobalt system has been developed using an enone as a mild oxidant. Mechanistic studies revealed that it proceeds through a Co(i)-catalyzed hydrogen-transfer route, wherein the α-vinyl moiety in the bidentate enone functions as a hydride acceptor. Meanwhile, Co(i)-catalyzed formyl C-H activation occurred as a competing reaction leading to aldehyde dimerization. The occurrence of the usually kinetically disfavored hydride transfer step therein was significantly increased in the presence of an enone reacting as a hydride transfer initiator.

Original language	English
Pages (from-to)	801-807
Number of pages	7
Journal	Organic Chemistry Frontiers
Volume	6
Issue number	6
DOIs	https://doi.org/10.1039/c8qo01298a
Publication status	Published - 21 Mar 2019
Externally published	Yes

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title = "Cobalt-catalyzed direct transformation of aldehydes to esters: The crucial role of an enone as a mediator",

abstract = "An oxidative esterification of aldehydes with alkanols catalyzed by an in situ generated low-valent cobalt system has been developed using an enone as a mild oxidant. Mechanistic studies revealed that it proceeds through a Co(i)-catalyzed hydrogen-transfer route, wherein the α-vinyl moiety in the bidentate enone functions as a hydride acceptor. Meanwhile, Co(i)-catalyzed formyl C-H activation occurred as a competing reaction leading to aldehyde dimerization. The occurrence of the usually kinetically disfavored hydride transfer step therein was significantly increased in the presence of an enone reacting as a hydride transfer initiator.",

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AU - Jiang, Biao Lin

AU - Lin, Yang

AU - Wang, Meng Liang

AU - Liu, Dian Sheng

AU - Xu, Bao Hua

AU - Zhang, Suo Jiang

PY - 2019/3/21

Y1 - 2019/3/21

N2 - An oxidative esterification of aldehydes with alkanols catalyzed by an in situ generated low-valent cobalt system has been developed using an enone as a mild oxidant. Mechanistic studies revealed that it proceeds through a Co(i)-catalyzed hydrogen-transfer route, wherein the α-vinyl moiety in the bidentate enone functions as a hydride acceptor. Meanwhile, Co(i)-catalyzed formyl C-H activation occurred as a competing reaction leading to aldehyde dimerization. The occurrence of the usually kinetically disfavored hydride transfer step therein was significantly increased in the presence of an enone reacting as a hydride transfer initiator.

AB - An oxidative esterification of aldehydes with alkanols catalyzed by an in situ generated low-valent cobalt system has been developed using an enone as a mild oxidant. Mechanistic studies revealed that it proceeds through a Co(i)-catalyzed hydrogen-transfer route, wherein the α-vinyl moiety in the bidentate enone functions as a hydride acceptor. Meanwhile, Co(i)-catalyzed formyl C-H activation occurred as a competing reaction leading to aldehyde dimerization. The occurrence of the usually kinetically disfavored hydride transfer step therein was significantly increased in the presence of an enone reacting as a hydride transfer initiator.

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Cobalt-catalyzed direct transformation of aldehydes to esters: The crucial role of an enone as a mediator

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