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. 2017 Oct 25;139(42):14857-14860.
doi: 10.1021/jacs.7b08459. Epub 2017 Oct 12.

General, Auxiliary-Enabled Photoinduced Pd-Catalyzed Remote Desaturation of Aliphatic Alcohols

Marvin Parasram  1 , Padon Chuentragool  1 , Yang Wang  1 , Yi Shi  1 , Vladimir Gevorgyan  1
Affiliations

General, Auxiliary-Enabled Photoinduced Pd-Catalyzed Remote Desaturation of Aliphatic Alcohols

Marvin Parasram et al. J Am Chem Soc. .

Abstract

A general, efficient, and site-selective visible light-induced Pd-catalyzed remote desaturation of aliphatic alcohols into valuable allylic, homoallylic, and bis-homoallylic alcohols has been developed. This transformation operates via a hybrid Pd-radical mechanism, which synergistically combines the favorable features of radical approaches, such as a facile remote C-H HAT step, with that of transition-metal-catalyzed chemistry (selective β-hydrogen elimination step). This allows achieving superior degrees of regioselectivity and yields in the desaturation of alcohols compared to those obtained by the state-of-the-art desaturation methods. The HAT at unactivated C(sp3)-H sites is enabled by the easily installable/removable Si-auxiliaries. Formation of the key hybrid alkyl Pd-radical intermediates is efficiently induced by visible light from alkyl iodides and Pd(0) complexes. Notably, this method requires no exogenous photosensitizers or external oxidants.

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Conflict of interest statement

Notes

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1
Desaturations Methods in Aliphatic Systems
Scheme 2
Scheme 2
Comparison Study
Scheme 3
Scheme 3
Proposed Mechanism
See this image and copyright information in PMC

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