Cobalt-Catalyzed Dehydrogenative Coupling of Alcohols/Aldehydes and Amines: An Important Role for Imine Hydration

Ya Fei Guo; Tian Lu Ren; Bao Hua Xu; Yao Feng Wang; Suo Jiang Zhang

doi:10.1002/ajoc.201500514

Cobalt-Catalyzed Dehydrogenative Coupling of Alcohols/Aldehydes and Amines: An Important Role for Imine Hydration

Ya Fei Guo, Tian Lu Ren, Bao Hua Xu^*, Yao Feng Wang, Suo Jiang Zhang

^*Corresponding author for this work

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

15 Citations (Scopus)

Abstract

A cobalt and iodide co-catalyzed oxidative amidation reaction between alcohols or aldehydes and amines has been developed. The reactions proceeded smoothly under mild conditions using tert-butyl hydroperoxide solution in water as the terminal oxidant, with broad functional group tolerance. Mechanistic studies indicated that the tBuO/tBuOO radical generated insitu is the active species responsible for hydrogen abstraction in this catalytic process, and not IO^-/IO₂ ^-/IO₃ ^- ions. Investigation into the reaction mechanism also revealed the potential transiency of a hemiaminal and the important role of its regeneration by imine hydration. A good hyd-ing: A protocol for Co^II/I^-/tert-butyl hydroperoxide-catalyzed oxidative cross-coupling of alcohols or aldehydes with amines has been developed. tBuO/tBuOO rather than IO^-/IO₂ ^-/IO₃ ^- is the active hydrogen-abstraction species in this catalytic process. Investigation into the reaction mechanism also revealed the potential transiency of a hemiaminal and the important role of its regeneration by imine hydration.

Original language	English
Pages (from-to)	568-574
Number of pages	7
Journal	Asian Journal of Organic Chemistry
Volume	5
Issue number	4
DOIs	https://doi.org/10.1002/ajoc.201500514
Publication status	Published - 1 Apr 2016
Externally published	Yes

Keywords

Cobalt
Cooperative catalysis
Iminehydration
Iodides
Oxidative amidation

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10.1002/ajoc.201500514

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title = "Cobalt-Catalyzed Dehydrogenative Coupling of Alcohols/Aldehydes and Amines: An Important Role for Imine Hydration",

abstract = "A cobalt and iodide co-catalyzed oxidative amidation reaction between alcohols or aldehydes and amines has been developed. The reactions proceeded smoothly under mild conditions using tert-butyl hydroperoxide solution in water as the terminal oxidant, with broad functional group tolerance. Mechanistic studies indicated that the tBuO/tBuOO radical generated insitu is the active species responsible for hydrogen abstraction in this catalytic process, and not IO-/IO2 -/IO3 - ions. Investigation into the reaction mechanism also revealed the potential transiency of a hemiaminal and the important role of its regeneration by imine hydration. A good hyd-ing: A protocol for CoII/I-/tert-butyl hydroperoxide-catalyzed oxidative cross-coupling of alcohols or aldehydes with amines has been developed. tBuO/tBuOO rather than IO-/IO2 -/IO3 - is the active hydrogen-abstraction species in this catalytic process. Investigation into the reaction mechanism also revealed the potential transiency of a hemiaminal and the important role of its regeneration by imine hydration.",

keywords = "Cobalt, Cooperative catalysis, Iminehydration, Iodides, Oxidative amidation",

author = "Guo, \{Ya Fei\} and Ren, \{Tian Lu\} and Xu, \{Bao Hua\} and Wang, \{Yao Feng\} and Zhang, \{Suo Jiang\}",

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year = "2016",

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T1 - Cobalt-Catalyzed Dehydrogenative Coupling of Alcohols/Aldehydes and Amines

T2 - An Important Role for Imine Hydration

AU - Guo, Ya Fei

AU - Ren, Tian Lu

AU - Xu, Bao Hua

AU - Wang, Yao Feng

AU - Zhang, Suo Jiang

PY - 2016/4/1

Y1 - 2016/4/1

N2 - A cobalt and iodide co-catalyzed oxidative amidation reaction between alcohols or aldehydes and amines has been developed. The reactions proceeded smoothly under mild conditions using tert-butyl hydroperoxide solution in water as the terminal oxidant, with broad functional group tolerance. Mechanistic studies indicated that the tBuO/tBuOO radical generated insitu is the active species responsible for hydrogen abstraction in this catalytic process, and not IO-/IO2 -/IO3 - ions. Investigation into the reaction mechanism also revealed the potential transiency of a hemiaminal and the important role of its regeneration by imine hydration. A good hyd-ing: A protocol for CoII/I-/tert-butyl hydroperoxide-catalyzed oxidative cross-coupling of alcohols or aldehydes with amines has been developed. tBuO/tBuOO rather than IO-/IO2 -/IO3 - is the active hydrogen-abstraction species in this catalytic process. Investigation into the reaction mechanism also revealed the potential transiency of a hemiaminal and the important role of its regeneration by imine hydration.

AB - A cobalt and iodide co-catalyzed oxidative amidation reaction between alcohols or aldehydes and amines has been developed. The reactions proceeded smoothly under mild conditions using tert-butyl hydroperoxide solution in water as the terminal oxidant, with broad functional group tolerance. Mechanistic studies indicated that the tBuO/tBuOO radical generated insitu is the active species responsible for hydrogen abstraction in this catalytic process, and not IO-/IO2 -/IO3 - ions. Investigation into the reaction mechanism also revealed the potential transiency of a hemiaminal and the important role of its regeneration by imine hydration. A good hyd-ing: A protocol for CoII/I-/tert-butyl hydroperoxide-catalyzed oxidative cross-coupling of alcohols or aldehydes with amines has been developed. tBuO/tBuOO rather than IO-/IO2 -/IO3 - is the active hydrogen-abstraction species in this catalytic process. Investigation into the reaction mechanism also revealed the potential transiency of a hemiaminal and the important role of its regeneration by imine hydration.

KW - Cobalt

KW - Cooperative catalysis

KW - Iminehydration

KW - Iodides

KW - Oxidative amidation

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ER -

Cobalt-Catalyzed Dehydrogenative Coupling of Alcohols/Aldehydes and Amines: An Important Role for Imine Hydration

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