TY - JOUR
T1 - General, Mild, and Selective Method for Desaturation of Aliphatic Amines
AU - Chuentragool, Padon
AU - Parasram, Marvin
AU - Shi, Yi
AU - Gevorgyan, Vladimir
N1 - Funding Information:
We thank the National Institutes of Health (GM120281) for financial support of this work. We also thank Dr. Yang Wang (Northwestern University) for helpful discussions.
Publisher Copyright:
© 2018 American Chemical Society.
PY - 2018/2/21
Y1 - 2018/2/21
N2 - A novel method for desaturation of aliphatic amines into enamines as well as allylic and homoallylic amines has been developed. This general protocol operates via putative aryl hybrid Pd-radical intermediates, which combine the signature features of radical chemistry, a hydrogen atom transfer (HAT) process, and transition metal chemistry, a selective β-hydride elimination step, to achieve efficient and selective desaturation of amines. These hybrid Pd-radical intermediates are efficiently generated under mild photoinduced conditions and are capable of a 1,n-HAT (n = 5-7) event at C(sp3)-H sites. The selectivity of HAT is tunable by varying different auxiliaries, which highlight the generality of this method. Remarkably, this desaturation method, which operates under mild conditions and does not require employment of exogenous photosensitizers or oxidants, can be performed in a practical scalable fashion from simple amines.
AB - A novel method for desaturation of aliphatic amines into enamines as well as allylic and homoallylic amines has been developed. This general protocol operates via putative aryl hybrid Pd-radical intermediates, which combine the signature features of radical chemistry, a hydrogen atom transfer (HAT) process, and transition metal chemistry, a selective β-hydride elimination step, to achieve efficient and selective desaturation of amines. These hybrid Pd-radical intermediates are efficiently generated under mild photoinduced conditions and are capable of a 1,n-HAT (n = 5-7) event at C(sp3)-H sites. The selectivity of HAT is tunable by varying different auxiliaries, which highlight the generality of this method. Remarkably, this desaturation method, which operates under mild conditions and does not require employment of exogenous photosensitizers or oxidants, can be performed in a practical scalable fashion from simple amines.
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U2 - 10.1021/jacs.8b00488
DO - 10.1021/jacs.8b00488
M3 - Article
C2 - 29400959
AN - SCOPUS:85042386709
SN - 0002-7863
VL - 140
SP - 2465
EP - 2468
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 7
ER -