Following an ISES lead: the first examples of asymmetric Ni(0)-mediated allylic amination

Org Lett. 2004 Aug 5;6(16):2661-4. doi: 10.1021/ol049159x.

Abstract

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

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.
  • Research Support, U.S. Gov't, P.H.S.

MeSH terms

  • Amination
  • Catalysis
  • Enzyme Inhibitors / chemical synthesis*
  • Glycine / analogs & derivatives*
  • Glycine / chemical synthesis*
  • Nickel / chemistry*
  • Phosphines / chemistry
  • Pyridoxal Phosphate

Substances

  • Enzyme Inhibitors
  • Phosphines
  • vinylglycine
  • Pyridoxal Phosphate
  • Nickel
  • Glycine