TY - JOUR
T1 - General, Auxiliary-Enabled Photoinduced Pd-Catalyzed Remote Desaturation of Aliphatic Alcohols
AU - Parasram, Marvin
AU - Chuentragool, Padon
AU - Wang, Yang
AU - Shi, Yi
AU - Gevorgyan, Vladimir
N1 - Funding Information:
This research was supported by the National Science Foundation (CHE-1663779) and the National Institutes of Health (GM120281). We also thank Ms. Jenny S. Martinez for help with graphical image.
Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/10/25
Y1 - 2017/10/25
N2 - 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.
AB - 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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U2 - 10.1021/jacs.7b08459
DO - 10.1021/jacs.7b08459
M3 - Article
C2 - 28992686
AN - SCOPUS:85032274131
SN - 0002-7863
VL - 139
SP - 14857
EP - 14860
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 42
ER -