Following an ISES lead: the first examples of asymmetric Ni(0)-mediated allylic amination.
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]
Department of Chemistry, University of Nebraska, Lincoln, NE 68588-0304, USA. dbb@unlserve.unl.edu
David B
DB
Berkowitz
Gourhari
G
Maiti
D000586:Amination; D002384:Catalysis; D004791:Enzyme Inhibitors / Q000138:chemical synthesis*; D005998:Glycine / Q000031:analogs & derivatives* / Q000138:chemical synthesis*; D009532:Nickel / Q000737:chemistry*; D010720:Phosphines / Q000737:chemistry; D011732:Pyridoxal Phosphate
D004791:Enzyme Inhibitors; D010720:Phosphines; C006507:vinylglycine; D011732:Pyridoxal Phosphate; D009532:Nickel; D005998:Glycine