Chemistry and Chemical Bioengineering Unit, Okinawa Institute of Science and Technology Graduate University, 1919-1 Tancha, Onna, Okinawa, 904-0495, Japan.
Angew Chem Int Ed Engl. 2021 Sep 20;60(39):21256-21260. doi: 10.1002/anie.202108734. Epub 2021 Aug 20.
Dynamic kinetic asymmetric transformation (DYKAT) reactions of racemic diastereomer mixtures that afford the products as essentially single diastereomers with high enantioselectivities are described. We demonstrated the DYKAT in the diastereo- and enantioselective synthesis of spirooxindoles bearing furan-fused rings. The starting materials of the DYKAT, dihydrobenzofuranone derivatives, were synthesized in racemic diastereomer mixtures, and these were transformed to the spirooxindole derivatives in high yields with high diastereo- and enantioselectivities through Michael-Henry cascade reactions with nitrostyrenes under organocatalytic conditions. In the reactions, regardless the stereochemistry of the starting materials, all the four isomers were transformed to single diastereomers with high enantioselectivities, and four new chiral centers were created.
描述了对映体混合物的动态动力学不对称转化（DYKAT）反应，这些反应以高对映选择性提供基本上为单一非对映异构体的产物。我们在具有呋喃稠合环的螺环氧化吲哚的对映选择性和非对映选择性合成中展示了 DYKAT。DYKAT 的起始材料二氢苯并呋喃酮衍生物以对映体混合物的形式合成，并且在有机催化条件下通过迈克尔-亨利于硝基苯乙烯的加成反应以高产率和高非对映选择性转化为螺环氧化吲哚衍生物。在反应中，无论起始材料的立体化学如何，所有四个异构体都以高对映选择性转化为单一非对映异构体，并创建了四个新的手性中心。
