TY - JOUR
T1 - Chemo- and Enantioselective Hydrogenation of α-Formyl Enamides
T2 - An Efficient Access to Chiral α-Amido Aldehydes
AU - Zhang, Jian
AU - Jia, Jia
AU - Zeng, Xincheng
AU - Wang, Yuanhao
AU - Zhang, Zhenfeng
AU - Gridnev, Ilya D.
AU - Zhang, Wanbin
N1 - Funding Information:
This work was partially supported by Shanghai Municipal Education Commission (No. 201701070002E00030) and National Natural Science Foundation of China (No. 21620102003, 21831005, 91856106, and 21572131). We thank the Instrumental Analysis Center of Shanghai Jiao Tong University. We acknowledge the generous gifts of the P-stereogenic bisphosphine ligands from Nippon Chemical Industrial Co. Ltd.
Publisher Copyright:
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2019/8/12
Y1 - 2019/8/12
N2 - In order to effectively synthesize chiral α-amino aldehydes, which have a wide range of potential applications in organic synthesis and medicinal chemistry, a highly chemo- and enantioselective hydrogenation of α-formyl enamides has been developed, catalyzed by a rhodium complex of a P-stereogenic bisphosphine ligand. Under different hydrogen pressures, the chiral α-amido aldehydes and β-amido alcohols were obtained in high yields (97–99 %) and with excellent chemo- and enantioselectivities (up to >99.9 % ee). The hydrogenation can be carried out on a gram scale and with a high substrate/catalyst ratio (up to 20 000 S/C), and the hydrogenated products were further converted into several important chiral products. Computations of the catalytic cycle gave a clear description for the R/S pathways, provided a reasonable explanation for the enantioselectivity, and revealed several other specific features.
AB - In order to effectively synthesize chiral α-amino aldehydes, which have a wide range of potential applications in organic synthesis and medicinal chemistry, a highly chemo- and enantioselective hydrogenation of α-formyl enamides has been developed, catalyzed by a rhodium complex of a P-stereogenic bisphosphine ligand. Under different hydrogen pressures, the chiral α-amido aldehydes and β-amido alcohols were obtained in high yields (97–99 %) and with excellent chemo- and enantioselectivities (up to >99.9 % ee). The hydrogenation can be carried out on a gram scale and with a high substrate/catalyst ratio (up to 20 000 S/C), and the hydrogenated products were further converted into several important chiral products. Computations of the catalytic cycle gave a clear description for the R/S pathways, provided a reasonable explanation for the enantioselectivity, and revealed several other specific features.
KW - chemoselectivity
KW - enantioselectivity
KW - homogeneous catalysis
KW - hydrogenation
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U2 - 10.1002/anie.201905263
DO - 10.1002/anie.201905263
M3 - Article
C2 - 31190338
AN - SCOPUS:85068854878
VL - 58
SP - 11505
EP - 11512
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
SN - 1433-7851
IS - 33
ER -