Chemo- and Enantioselective Hydrogenation of α-Formyl Enamides: An Efficient Access to Chiral α-Amido Aldehydes
Jian Zhang
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Pharmacy, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240 China
Search for more papers by this authorJia Jia
School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240 China
Search for more papers by this authorXincheng Zeng
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Pharmacy, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240 China
Search for more papers by this authorYuanhao Wang
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Pharmacy, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240 China
Search for more papers by this authorDr. Zhenfeng Zhang
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Pharmacy, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240 China
Search for more papers by this authorProf. Dr. Ilya D. Gridnev
Department of Chemistry, Graduate School of Science, Tohoku University, Aramaki 3–6, Aoba-ku, Sendai, 980-8578 Japan
Search for more papers by this authorCorresponding Author
Prof. Dr. Wanbin Zhang
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Pharmacy, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240 China
School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240 China
Search for more papers by this authorJian Zhang
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Pharmacy, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240 China
Search for more papers by this authorJia Jia
School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240 China
Search for more papers by this authorXincheng Zeng
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Pharmacy, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240 China
Search for more papers by this authorYuanhao Wang
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Pharmacy, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240 China
Search for more papers by this authorDr. Zhenfeng Zhang
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Pharmacy, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240 China
Search for more papers by this authorProf. Dr. Ilya D. Gridnev
Department of Chemistry, Graduate School of Science, Tohoku University, Aramaki 3–6, Aoba-ku, Sendai, 980-8578 Japan
Search for more papers by this authorCorresponding Author
Prof. Dr. Wanbin Zhang
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Pharmacy, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240 China
School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240 China
Search for more papers by this authorGraphical Abstract
A new arrow in the quiver: A highly chemo- and enantioselective hydrogenation of α-formyl enamides has been developed for the synthesis of chiral α-amido aldehydes in high yields (98–99 %), with excellent chemo- and enantioselectivities (up to >99.9 % ee), and with high substrate/catalyst ratios (up to 20000 S/C). Computations give a clear description of the R/S pathways of the catalytic cycle.
Abstract
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.
Conflict of interest
The authors declare no conflict of interest.
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