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. 2016 May 25;138(20):6340-3.
doi: 10.1021/jacs.6b01628. Epub 2016 May 10.

Photoinduced Formation of Hybrid Aryl Pd-Radical Species Capable of 1,5-HAT: Selective Catalytic Oxidation of Silyl Ethers into Silyl Enol Ethers

Marvin Parasram  1 , Padon Chuentragool  1 , Dhruba Sarkar  1 , Vladimir Gevorgyan  1
Affiliations

Photoinduced Formation of Hybrid Aryl Pd-Radical Species Capable of 1,5-HAT: Selective Catalytic Oxidation of Silyl Ethers into Silyl Enol Ethers

Marvin Parasram et al. J Am Chem Soc. .

Abstract

A direct visible light-induced generation of a hybrid aryl Pd-radical species from aryl iodide and Pd(0) is reported to enable an unprecedented (for hybrid Pd-radical species) hydrogen atom-transfer event. This approach allowed for efficient desaturation of readily available silyl ethers into synthetically valuable silyl enols. Moreover, this oxidation reaction proceeds at room temperature without the aid of exogenous photosensitizers or oxidants.

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Conflict of interest statement

Notes

The authors declare no competing financial interest.

ASSOCIATED CONTENT

Supporting Information

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/jacs.6b01628.

Experimental details and data (PDF)

Figures

Scheme 1.
Scheme 1.
Traditional and Proposed Novel Reactivity of Aryl Halides in Pd(0)-Catalyzed Reactions
Scheme 2.
Scheme 2.
Possible Mechanisms
Scheme 3.
Scheme 3.
Radical Clock Experiment
See this image and copyright information in PMC

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