Division of Applied Chemistry and Frontier Chemistry Center, Faculty of Engineering, Hokkaido University, Sapporo, Hokkaido, 060-8628, Japan.
Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Sapporo, Hokkaido, 060-8628, Japan.
Angew Chem Int Ed Engl. 2019 Aug 26;58(35):11998-12003. doi: 10.1002/anie.201906283. Epub 2019 Jul 16.
The first catalytic method for diastereo- and enantioselective synthesis of allylic boronates bearing a Z-trisubstituted alkenyl fluoride is disclosed. Boryl substitution is performed with either a Z- or E-allyldifluoride and is catalyzed by bisphosphine/Cu complexes, affording products in up to 99 % yield with >98:2 Z/E selectivity and 99:1 enantiomeric ratio. A variety of subsequent modifications are feasible, and notable examples are diastereoselective additions to aldehydes/aldimines to access homoallylic alcohols/amines containing a fluorosubstituted stereogenic quaternary center.
首次公开了一种对具有 Z-三取代烯基氟化物的烯丙基硼酸酯进行非对映选择性和对映选择性合成的催化方法。通过双膦/Cu 配合物进行硼取代,无论是 Z-或 E-烯丙基二氟化物都可进行取代,产物的收率高达 99%,Z/E 选择性>98:2,对映体过量值为 99:1。随后可进行多种修饰,其中显著的例子是与醛/亚胺进行非对映选择性加成,以获得含有氟取代的立体手性季碳中心的高烯丙醇/胺。