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

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

David B Berkowitz  1 , Gourhari Maiti
Affiliations

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

David B Berkowitz et al. Org Lett. .

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]

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Figures

Figure 1
Figure 1
UV/vis Traces for the ISES Data in Table 1.
Figure 2
Figure 2
Array of Chiral Bidentate Phosphine Ligands Examined
Scheme 1
Scheme 1
Synthesis of the Vigabatrin Precursor
Scheme 2
Scheme 2
A Ni(0)-Mediated Synthesis of L-Vinylglycine
See this image and copyright information in PMC

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