Chloroform as a hydrogen atom donor in barton reductive decarboxylation reactions

Junming Ho; Jingjing Zheng; Rubén Meana-Pañeda; Donald G. Truhlar; Eun Jung Ko; G. Paul Savage; Craig M. Williams; Michelle L. Coote; John Tsanaktsidis

doi:10.1021/jo400927y

Chloroform as a hydrogen atom donor in barton reductive decarboxylation reactions

Junming Ho, Jingjing Zheng, Rubén Meana-Pañeda, Donald G. Truhlar^*, Eun Jung Ko, G. Paul Savage, Craig M. Williams, Michelle L. Coote, John Tsanaktsidis

^*Corresponding author for this work

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

43 Citations (Scopus)

Abstract

The utility of chloroform as both a solvent and a hydrogen atom donor in Barton reductive decarboxylation of a range of carboxylic acids was recently demonstrated (Ko, E. J. et al. Org. Lett. 2011, 13, 1944). In the present work, a combination of electronic structure calculations, direct dynamics calculations, and experimental studies was carried out to investigate how chloroform acts as a hydrogen atom donor in Barton reductive decarboxylations and to determine the scope of this process. The results from this study show that hydrogen atom transfer from chloroform occurs directly under kinetic control and is aided by a combination of polar effects and quantum mechanical tunneling. Chloroform acts as an effective hydrogen atom donor for primary, secondary, and tertiary alkyl radicals, although significant chlorination was also observed with unstrained tertiary carboxylic acids.

Original language	English
Pages (from-to)	6677-6687
Number of pages	11
Journal	Journal of Organic Chemistry
Volume	78
Issue number	13
DOIs	https://doi.org/10.1021/jo400927y
Publication status	Published - 5 Jul 2013

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title = "Chloroform as a hydrogen atom donor in barton reductive decarboxylation reactions",

abstract = "The utility of chloroform as both a solvent and a hydrogen atom donor in Barton reductive decarboxylation of a range of carboxylic acids was recently demonstrated (Ko, E. J. et al. Org. Lett. 2011, 13, 1944). In the present work, a combination of electronic structure calculations, direct dynamics calculations, and experimental studies was carried out to investigate how chloroform acts as a hydrogen atom donor in Barton reductive decarboxylations and to determine the scope of this process. The results from this study show that hydrogen atom transfer from chloroform occurs directly under kinetic control and is aided by a combination of polar effects and quantum mechanical tunneling. Chloroform acts as an effective hydrogen atom donor for primary, secondary, and tertiary alkyl radicals, although significant chlorination was also observed with unstrained tertiary carboxylic acids.",

author = "Junming Ho and Jingjing Zheng and Rub{\'e}n Meana-Pa{\~n}eda and Truhlar, {Donald G.} and Ko, {Eun Jung} and Savage, {G. Paul} and Williams, {Craig M.} and Coote, {Michelle L.} and John Tsanaktsidis",

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TY - JOUR

T1 - Chloroform as a hydrogen atom donor in barton reductive decarboxylation reactions

AU - Ho, Junming

AU - Zheng, Jingjing

AU - Meana-Pañeda, Rubén

AU - Truhlar, Donald G.

AU - Ko, Eun Jung

AU - Savage, G. Paul

AU - Williams, Craig M.

AU - Coote, Michelle L.

AU - Tsanaktsidis, John

PY - 2013/7/5

Y1 - 2013/7/5

N2 - The utility of chloroform as both a solvent and a hydrogen atom donor in Barton reductive decarboxylation of a range of carboxylic acids was recently demonstrated (Ko, E. J. et al. Org. Lett. 2011, 13, 1944). In the present work, a combination of electronic structure calculations, direct dynamics calculations, and experimental studies was carried out to investigate how chloroform acts as a hydrogen atom donor in Barton reductive decarboxylations and to determine the scope of this process. The results from this study show that hydrogen atom transfer from chloroform occurs directly under kinetic control and is aided by a combination of polar effects and quantum mechanical tunneling. Chloroform acts as an effective hydrogen atom donor for primary, secondary, and tertiary alkyl radicals, although significant chlorination was also observed with unstrained tertiary carboxylic acids.

AB - The utility of chloroform as both a solvent and a hydrogen atom donor in Barton reductive decarboxylation of a range of carboxylic acids was recently demonstrated (Ko, E. J. et al. Org. Lett. 2011, 13, 1944). In the present work, a combination of electronic structure calculations, direct dynamics calculations, and experimental studies was carried out to investigate how chloroform acts as a hydrogen atom donor in Barton reductive decarboxylations and to determine the scope of this process. The results from this study show that hydrogen atom transfer from chloroform occurs directly under kinetic control and is aided by a combination of polar effects and quantum mechanical tunneling. Chloroform acts as an effective hydrogen atom donor for primary, secondary, and tertiary alkyl radicals, although significant chlorination was also observed with unstrained tertiary carboxylic acids.

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JF - Journal of Organic Chemistry

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ER -

Chloroform as a hydrogen atom donor in barton reductive decarboxylation reactions

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