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. 2016 Aug 31;138(34):10794-7.
doi: 10.1021/jacs.6b06517. Epub 2016 Aug 18.

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

Hatice G Yayla  1 , Huaiju Wang  1 , Kyle T Tarantino  1 , Hudson S Orbe  1 , Robert R Knowles  1
Affiliations

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

Hatice G Yayla et al. J Am Chem Soc. .

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.

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Conflict of interest statement

The authors declare no competing financial interests.

Figures

Figure 1
Figure 1
Catalytic ring opening of cyclic alcohols via PCET
Figure 2
Figure 2
Proposed catalytic cycle
Figure 3
Figure 3
Distal C-C bonds cleaved via long-range PCET
Figure 4
Figure 4
Effective BDFE correlations with reactivity
See this image and copyright information in PMC

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