Direct Catalytic Addition of Alkylnitriles to Aldehydes by Transition‐Metal/NHC Complexes |
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| Authors: | Dr Devarajulu Sureshkumar Dr Venkataraman Ganesh Dr Naoya Kumagai Prof?Dr Masakatsu Shibasaki |
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| Affiliation: | 1. Institute of Microbial Chemistry (BIKAKEN), Tokyo, 3‐14‐23 Kamiosaki, Shinagawa‐ku, Tokyo 141‐0021 (Japan);2. JST, ACT‐C, 3‐14‐23 Kamiosaki, Shinagawa‐ku, Tokyo 141‐0021 (Japan) |
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| Abstract: | Direct catalytic addition of alkylnitriles to aldehydes allows for an atom‐economical access to β‐hydroxynitriles under proton transfer conditions. Direct use of alkylnitriles as pronucleophiles has been hampered due to their low acidity resulting in an inability to generate α‐cyano carbanions in a catalytic manner. A transition metal/N‐heterocyclic carbene (NHC) complex prepared from {Rh(OMe)(cod)}2] and an imidazolium‐based carbene was identified as an effective catalyst to promote the reaction with as little as 1.25 mol % of catalyst loading. The corresponding Rh complex, derived from chiral triazolium salt, rendered the reaction enantioselective, albeit with moderate enantioselectivity. |
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| Keywords: | alkylnitriles asymmetric catalysis cooperative catalysis N‐heterocyclic carbenes rhodium |
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