Catalytic Ring-Opening of Cyclic Alcohols Enabled by PCET Activation of Strong O-H Bonds

Hatice G. Yayla; Huaiju Wang; Kyle T. Tarantino; Hudson S. Orbe; Robert R. Knowles

doi:10.1021/jacs.6b06517

Catalytic Ring-Opening of Cyclic Alcohols Enabled by PCET Activation of Strong O-H Bonds

Hatice G. Yayla, Huaiju Wang, Kyle T. Tarantino, Hudson S. Orbe, Robert R. Knowles

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

244 Scopus citations

Abstract

We report a new photocatalytic protocol for the redox-neutral isomerization of cyclic alcohols to linear ketones via C-C bond scission. Mechanistic studies demonstrate that key alkoxy radical intermediates in this reaction are generated via the direct homolytic activation of alcohol O-H bonds in an unusual intramolecular PCET process, wherein the electron travels to a proximal radical cation in concert with proton transfer to a weak Brønsted base. Effective bond strength considerations are shown to accurately forecast the feasibility of alkoxy radical generation with a given oxidant/base pair.

Original language	English (US)
Pages (from-to)	10794-10797
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	138
Issue number	34
DOIs	https://doi.org/10.1021/jacs.6b06517
State	Published - Aug 31 2016

All Science Journal Classification (ASJC) codes

Chemistry(all)
Biochemistry
Catalysis
Colloid and Surface Chemistry

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10.1021/jacs.6b06517

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title = "Catalytic Ring-Opening of Cyclic Alcohols Enabled by PCET Activation of Strong O-H Bonds",

abstract = "We report a new photocatalytic protocol for the redox-neutral isomerization of cyclic alcohols to linear ketones via C-C bond scission. Mechanistic studies demonstrate that key alkoxy radical intermediates in this reaction are generated via the direct homolytic activation of alcohol O-H bonds in an unusual intramolecular PCET process, wherein the electron travels to a proximal radical cation in concert with proton transfer to a weak Br{\o}nsted base. Effective bond strength considerations are shown to accurately forecast the feasibility of alkoxy radical generation with a given oxidant/base pair.",

author = "Yayla, {Hatice G.} and Huaiju Wang and Tarantino, {Kyle T.} and Orbe, {Hudson S.} and Knowles, {Robert R.}",

note = "Funding Information: Financial support was provided by the NIH (R01 GM113105). bR.R.K is a fellow of the A. P. Sloan Foundation. We thank Istvan Pelczer for help with NMR experiments and Laura Wilson for help with sample purification. Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

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doi = "10.1021/jacs.6b06517",

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T1 - Catalytic Ring-Opening of Cyclic Alcohols Enabled by PCET Activation of Strong O-H Bonds

AU - Yayla, Hatice G.

AU - Wang, Huaiju

AU - Tarantino, Kyle T.

AU - Orbe, Hudson S.

AU - Knowles, Robert R.

N1 - Funding Information: Financial support was provided by the NIH (R01 GM113105). bR.R.K is a fellow of the A. P. Sloan Foundation. We thank Istvan Pelczer for help with NMR experiments and Laura Wilson for help with sample purification. Publisher Copyright: © 2016 American Chemical Society.

PY - 2016/8/31

Y1 - 2016/8/31

N2 - We report a new photocatalytic protocol for the redox-neutral isomerization of cyclic alcohols to linear ketones via C-C bond scission. Mechanistic studies demonstrate that key alkoxy radical intermediates in this reaction are generated via the direct homolytic activation of alcohol O-H bonds in an unusual intramolecular PCET process, wherein the electron travels to a proximal radical cation in concert with proton transfer to a weak Brønsted base. Effective bond strength considerations are shown to accurately forecast the feasibility of alkoxy radical generation with a given oxidant/base pair.

AB - We report a new photocatalytic protocol for the redox-neutral isomerization of cyclic alcohols to linear ketones via C-C bond scission. Mechanistic studies demonstrate that key alkoxy radical intermediates in this reaction are generated via the direct homolytic activation of alcohol O-H bonds in an unusual intramolecular PCET process, wherein the electron travels to a proximal radical cation in concert with proton transfer to a weak Brønsted base. Effective bond strength considerations are shown to accurately forecast the feasibility of alkoxy radical generation with a given oxidant/base pair.

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Catalytic Ring-Opening of Cyclic Alcohols Enabled by PCET Activation of Strong O-H Bonds

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