Following an ISES Lead:  The First\nExamples of Asymmetric Ni(0)-Mediated\nAllylic Amination

An ISES (in situ enzymatic screening) lead pointed to conditions (PMP N-protecting group, Ni(cod)₂ catalyst precursor) under which chiral,\nbidentate phosphines could promote Ni(0)-mediated allylic amination. Therefore, bidentate phosphines bearing central, axial, and planar chirality\nwere examined with two model substrates of interest for PLP-enzyme inhibitor synthesis. In the best case, with (<i>R</i>)-MeO-BIPHEP, vinylglycinol\nderivative <b>2</b> was obtained in 75% ee (97% ee, one recrystallization) from <b>1</b>. Further manipulation provided a Ni(0)-mediated entry into l-vinylglycine.