Cobalt(II)/TFA-Catalyzed Oxidative Esterification of Aldehydes and Alcohols: Dual Role of the Acid Co-Catalyst

Sajid Mahmood; Ting Li; Bao Hua Xu; Ya Fei Guo; Suo Jiang Zhang

doi:10.1002/ajoc.201700139

Cobalt(II)/TFA-Catalyzed Oxidative Esterification of Aldehydes and Alcohols: Dual Role of the Acid Co-Catalyst

Sajid Mahmood, Ting Li, Bao Hua Xu^*, Ya Fei Guo, Suo Jiang Zhang

^*Corresponding author for this work

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

14 Citations (Scopus)

Abstract

A Co^II/CF₃COOH (TFA)-catalyzed oxidative esterification of aldehydes and alkanols by using tBuOOH as an oxidant is reported. A mechanistic investigation indicated that the oxidation reaction proceeded through the formation of a Co^III−OCH(OMe)R complex, followed by H-atom abstraction by an in-situ-generated tBuO^. radical. The former kinetic step was thought to be the selectivity-determining step. Moreover, the strong acidity and TFA proton were beneficial for both the dehydrative formation of the Co^III−OCH(OMe)R complex and the redox properties of the cobalt atom, thereby offering high efficiency for the target oxidative cross-coupling reaction.

Original language	English
Pages (from-to)	768-774
Number of pages	7
Journal	Asian Journal of Organic Chemistry
Volume	6
Issue number	6
DOIs	https://doi.org/10.1002/ajoc.201700139
Publication status	Published - Jun 2017
Externally published	Yes

Keywords

cobalt
cross-coupling
esterification
oxidation
reaction mechanisms

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10.1002/ajoc.201700139

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title = "Cobalt(II)/TFA-Catalyzed Oxidative Esterification of Aldehydes and Alcohols: Dual Role of the Acid Co-Catalyst",

abstract = "A CoII/CF3COOH (TFA)-catalyzed oxidative esterification of aldehydes and alkanols by using tBuOOH as an oxidant is reported. A mechanistic investigation indicated that the oxidation reaction proceeded through the formation of a CoIII−OCH(OMe)R complex, followed by H-atom abstraction by an in-situ-generated tBuO. radical. The former kinetic step was thought to be the selectivity-determining step. Moreover, the strong acidity and TFA proton were beneficial for both the dehydrative formation of the CoIII−OCH(OMe)R complex and the redox properties of the cobalt atom, thereby offering high efficiency for the target oxidative cross-coupling reaction.",

keywords = "cobalt, cross-coupling, esterification, oxidation, reaction mechanisms",

author = "Sajid Mahmood and Ting Li and Xu, \{Bao Hua\} and Guo, \{Ya Fei\} and Zhang, \{Suo Jiang\}",

note = "Publisher Copyright: {\textcopyright} 2017 Wiley-VCH Verlag GmbH \& Co. KGaA, Weinheim",

year = "2017",

month = jun,

doi = "10.1002/ajoc.201700139",

language = "English",

volume = "6",

pages = "768--774",

journal = "Asian Journal of Organic Chemistry",

issn = "2193-5807",

publisher = "Wiley - VCH Verlag GmbH \& CO. KGaA",

number = "6",

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TY - JOUR

T1 - Cobalt(II)/TFA-Catalyzed Oxidative Esterification of Aldehydes and Alcohols

T2 - Dual Role of the Acid Co-Catalyst

AU - Mahmood, Sajid

AU - Li, Ting

AU - Xu, Bao Hua

AU - Guo, Ya Fei

AU - Zhang, Suo Jiang

PY - 2017/6

Y1 - 2017/6

N2 - A CoII/CF3COOH (TFA)-catalyzed oxidative esterification of aldehydes and alkanols by using tBuOOH as an oxidant is reported. A mechanistic investigation indicated that the oxidation reaction proceeded through the formation of a CoIII−OCH(OMe)R complex, followed by H-atom abstraction by an in-situ-generated tBuO. radical. The former kinetic step was thought to be the selectivity-determining step. Moreover, the strong acidity and TFA proton were beneficial for both the dehydrative formation of the CoIII−OCH(OMe)R complex and the redox properties of the cobalt atom, thereby offering high efficiency for the target oxidative cross-coupling reaction.

AB - A CoII/CF3COOH (TFA)-catalyzed oxidative esterification of aldehydes and alkanols by using tBuOOH as an oxidant is reported. A mechanistic investigation indicated that the oxidation reaction proceeded through the formation of a CoIII−OCH(OMe)R complex, followed by H-atom abstraction by an in-situ-generated tBuO. radical. The former kinetic step was thought to be the selectivity-determining step. Moreover, the strong acidity and TFA proton were beneficial for both the dehydrative formation of the CoIII−OCH(OMe)R complex and the redox properties of the cobalt atom, thereby offering high efficiency for the target oxidative cross-coupling reaction.

KW - cobalt

KW - cross-coupling

KW - esterification

KW - oxidation

KW - reaction mechanisms

UR - http://www.scopus.com/inward/record.url?scp=85018597086&partnerID=8YFLogxK

U2 - 10.1002/ajoc.201700139

DO - 10.1002/ajoc.201700139

M3 - Article

AN - SCOPUS:85018597086

SN - 2193-5807

VL - 6

SP - 768

EP - 774

JO - Asian Journal of Organic Chemistry

JF - Asian Journal of Organic Chemistry

IS - 6

ER -

Cobalt(II)/TFA-Catalyzed Oxidative Esterification of Aldehydes and Alcohols: Dual Role of the Acid Co-Catalyst

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Keywords

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