TY - JOUR
T1 - Rh(I)-Catalyzed Hydroamidation of Olefins via Selective Activation of N-H Bonds in Aliphatic Amines
AU - Dong, Kaiwu
AU - Fang, Xianjie
AU - Jackstell, Ralf
AU - Laurenczy, Gabor
AU - Li, Yuehui
AU - Beller, Matthias
N1 - Publisher Copyright:
© 2015 American Chemical Society.
PY - 2015/5/13
Y1 - 2015/5/13
N2 - Hydroamidation of olefins constitutes an ideal, atom-efficient method to prepare carboxylic amides from easily available olefins, CO, and amines. So far, aliphatic amines are not suitable for these transformations. Here, we present a ligand- and additive-free Rh(I) catalyst as solution to this problem. Various amides are obtained in good yields and excellent regioselectivities. Notably, chemoselective amidation of aliphatic amines takes place in the presence of aromatic amines and alcohols. Mechanistic studies reveal the presence of Rh-acyl species as crucial intermediates for the selectivity and rate-limiting step in the proposed Rh(I)-catalytic cycle. (Chemical Formula Presented).
AB - Hydroamidation of olefins constitutes an ideal, atom-efficient method to prepare carboxylic amides from easily available olefins, CO, and amines. So far, aliphatic amines are not suitable for these transformations. Here, we present a ligand- and additive-free Rh(I) catalyst as solution to this problem. Various amides are obtained in good yields and excellent regioselectivities. Notably, chemoselective amidation of aliphatic amines takes place in the presence of aromatic amines and alcohols. Mechanistic studies reveal the presence of Rh-acyl species as crucial intermediates for the selectivity and rate-limiting step in the proposed Rh(I)-catalytic cycle. (Chemical Formula Presented).
UR - https://www.scopus.com/pages/publications/84929376729
U2 - 10.1021/jacs.5b02218
DO - 10.1021/jacs.5b02218
M3 - 文章
AN - SCOPUS:84929376729
SN - 0002-7863
VL - 137
SP - 6053
EP - 6058
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 18
ER -