Yamashita Yasuhiro, Kobayashi Shū
Department of Chemistry, School of Science, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan.
Chemistry. 2018 Jan 2;24(1):10-17. doi: 10.1002/chem.201703404. Epub 2017 Nov 29.
Catalytic carbon-carbon bond-forming reactions of weakly acidic carbon pronucleophiles with N-aryl imines, α,β-unsaturated amides, and others under proton-transfer conditions were developed by designing strongly basic reaction intermediates known as product bases. The reactions proceed smoothly in the presence of a catalytic amount of strong base such as KH or alkaline metal amides. Modification of the metal cations by using chiral macrocyclic crown ethers allowed catalytic asymmetric 1,4-addition reactions to proceed with high enantioselectivities. This concept can be applied to Brønsted-base-catalyzed reactions of a wide range of weakly acidic carbon pronucleophiles.
通过设计被称为产物碱的强碱性反应中间体，开发了在质子转移条件下弱酸性碳亲核前体与N-芳基亚胺、α,β-不饱和酰胺等的催化碳-碳键形成反应。在催化量的强碱如KH或碱金属酰胺存在下，反应顺利进行。通过使用手性大环冠醚对金属阳离子进行修饰，可使催化不对称1,4-加成反应以高对映选择性进行。这一概念可应用于多种弱酸性碳亲核前体的布朗斯特碱催化反应。
