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

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

Research output: Contribution to journalArticle

37 Citations (Scopus)

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.

Original languageEnglish (US)
Pages (from-to)14857-14860
Number of pages4
JournalJournal of the American Chemical Society
Volume139
Issue number42
DOIs
StatePublished - Oct 25 2017
Externally publishedYes

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Alcohols
Light
Regioselectivity
Photosensitizing Agents
Photosensitizers
Iodides
Oxidants
Transition metals
Hydrogen
Metals

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

General, Auxiliary-Enabled Photoinduced Pd-Catalyzed Remote Desaturation of Aliphatic Alcohols. / Parasram, Marvin; Chuentragool, Padon; Wang, Yang; Shi, Yi; Gevorgyan, Vladimir.

In: Journal of the American Chemical Society, Vol. 139, No. 42, 25.10.2017, p. 14857-14860.

Research output: Contribution to journalArticle

Parasram, Marvin ; Chuentragool, Padon ; Wang, Yang ; Shi, Yi ; Gevorgyan, Vladimir. / General, Auxiliary-Enabled Photoinduced Pd-Catalyzed Remote Desaturation of Aliphatic Alcohols. In: Journal of the American Chemical Society. 2017 ; Vol. 139, No. 42. pp. 14857-14860.
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