Balázs László B, Huang Yinhua, Khalikuzzaman Jasmina B, Li Yongxin, Pullarkat Sumod A, Leung Pak-Hing
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371.
College of Material, Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou, China 311121.
J Org Chem. 2020 Nov 20;85(22):14763-14771. doi: 10.1021/acs.joc.0c00181. Epub 2020 Apr 3.
The asymmetric catalytic P-H addition of racemic secondary phosphines to electrophilic α-diazoesters via P*-N bond formation is disclosed for the first time. Interaction between the diazoester and the palladium catalyst resulted in the unusually enhanced electrophilic ability of the terminal nitrogen in the diazo functionality, as opposed to the commonly expected formation of a metal carbene by nitrogen elimination. Further derivatization of the generated phosphinic hydrazones provided access to enantioenriched P-stereogenic diarylphosphinates via a simple transformation.
