Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan.
J Org Chem. 2020 Oct 2;85(19):12703-12714. doi: 10.1021/acs.joc.0c01861. Epub 2020 Sep 22.
Ligand-controlled palladium-catalyzed divergent synthesis of isonitriles and nitriles from benzylic carbonates and TMSCN has been developed. The BINAP- or DPEphos-ligated palladium catalyst selectively provides the corresponding benzylic isonitriles, whereas their regioisomers, benzylic nitriles, are formed exclusively under phosphine ligand-free conditions. Mechanistic studies reveal that isonitrile is the primary product under both conditions, but it is isomerized into nitrile in the absence of ancillary phosphine ligands.
已开发出配体控制的钯催化从苄基碳酸酯和 TMSCN 到异腈和腈的发散合成方法。BINAP 或 DPEphos 配体化的钯催化剂选择性地提供相应的苄基异腈，而在无膦配体条件下则仅形成其区域异构体，苄基腈。机理研究表明，两种条件下都是异腈为主要产物，但在没有辅助膦配体的情况下，它会异构化为腈。
