Direct Catalytic Asymmetric Addition of Alkylnitriles to Aldehydes with Designed Nickel–Carbene Complexes
Dr. Akira Saito
Institute of Microbial Chemistry, 3-14-23 Kamiosaki, Shinagawa-ku, Tokyo, 141-0021 Japan
Search for more papers by this authorDr. Shinya Adachi
Institute of Microbial Chemistry, 3-14-23 Kamiosaki, Shinagawa-ku, Tokyo, 141-0021 Japan
Search for more papers by this authorCorresponding Author
Dr. Naoya Kumagai
Institute of Microbial Chemistry, 3-14-23 Kamiosaki, Shinagawa-ku, Tokyo, 141-0021 Japan
Search for more papers by this authorCorresponding Author
Prof. Dr. Masakatsu Shibasaki
Institute of Microbial Chemistry, 3-14-23 Kamiosaki, Shinagawa-ku, Tokyo, 141-0021 Japan
Search for more papers by this authorDr. Akira Saito
Institute of Microbial Chemistry, 3-14-23 Kamiosaki, Shinagawa-ku, Tokyo, 141-0021 Japan
Search for more papers by this authorDr. Shinya Adachi
Institute of Microbial Chemistry, 3-14-23 Kamiosaki, Shinagawa-ku, Tokyo, 141-0021 Japan
Search for more papers by this authorCorresponding Author
Dr. Naoya Kumagai
Institute of Microbial Chemistry, 3-14-23 Kamiosaki, Shinagawa-ku, Tokyo, 141-0021 Japan
Search for more papers by this authorCorresponding Author
Prof. Dr. Masakatsu Shibasaki
Institute of Microbial Chemistry, 3-14-23 Kamiosaki, Shinagawa-ku, Tokyo, 141-0021 Japan
Search for more papers by this authorGraphical Abstract
A direct catalytic asymmetric addition of acetonitrile to aldehydes with high enantioselectivity is achieved by the strategic use of a sterically demanding NiII pincer carbene complex. This afforded highly enantioenriched β-hydroxynitriles.
Abstract
A direct catalytic asymmetric addition of acetonitrile to aldehydes that realizes over 90 % ee is the ultimate challenge in alkylnitrile addition chemistry. Herein, we report achieving high enantioselectivity by the strategic use of a sterically demanding NiII pincer carbene complex, which afforded highly enantioenriched β-hydroxynitriles. This highly atom-economical process paves the way for exploiting inexpensive acetonitrile as a promising C2 building block in a practical synthetic toolbox for asymmetric catalysis.
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- 16The reaction using aliphatic aldehyde needs further development: the reaction of acetonitrile and cyclohexanecarboxaldehyde gave the corresponding product in 14 % yield (potassium salt of BHT was used instead of tBuOK, rt, 24 h).
- 17The reaction using ketone needs to be further development: methyl benzoylformate gave the corresponding product in 45 % yield and 45 % ee (w/o iPrOH, 0 °C, 24 h).
