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Chemo‐ and Enantioselective Hydrogenation of α‐Formyl Enamides: An Efficient Access to Chiral α‐Amido Aldehydes
Author(s) -
Zhang Jian,
Jia Jia,
Zeng Xincheng,
Wang Yuanhao,
Zhang Zhenfeng,
Gridnev Ilya D.,
Zhang Wanbin
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201905263
Subject(s) - stereocenter , enantioselective synthesis , catalysis , chemistry , asymmetric hydrogenation , organic chemistry , substrate (aquarium) , ligand (biochemistry) , rhodium , combinatorial chemistry , catalytic cycle , biochemistry , oceanography , receptor , geology
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.