Saito Akira, Adachi Shinya, Kumagai Naoya, Shibasaki Masakatsu
Institute of Microbial Chemistry, 3-14-23 Kamiosaki, Shinagawa-ku, Tokyo, 141-0021, Japan.
Angew Chem Int Ed Engl. 2021 Apr 12;60(16):8739-8743. doi: 10.1002/anie.202016690. Epub 2021 Mar 10.
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 Ni 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.
实现对映体过量（ee）超过90%的乙腈与醛的直接催化不对称加成是烷基腈加成化学中的终极挑战。在此，我们报告了通过策略性地使用空间位阻较大的镍钳形卡宾配合物实现了高对映选择性，该配合物可提供高度对映体富集的β-羟基腈。这一高度原子经济的过程为在不对称催化的实用合成工具箱中利用廉价的乙腈作为有前景的C2结构单元铺平了道路。
