Stereoselective radical addition of carbon-centred radicals to the dehydroalanine moiety of the chiral nickel(II) complex of the Schiff′s base derived from (S)-2-[N-(N′-benzylprolyl)amino]benzophenone and dehydroalanine

TLDR: In this paper, a new approach to the asymmetric synthesis of β-substituted α-aminopropanoic acids by 2,2′-azoisobutyronitrile (AIBN) and Bu3SnH-initiated radical addition of Etl, PriBr, ButBr, and PhCH2Br to the dehydroalanine moiety of the NiII complex 1 of a Schiff′s base derived from (S)-o-[N-(N′-benzylprolyl)amino]benzophenone

Abstract: A new approach to the asymmetric synthesis of β-substituted α-aminopropanoic acids by 2,2′-azoisobutyronitrile (AIBN) and Bu3SnH-initiated radical addition of Etl, PriBr, ButBr, and PhCH2Br to the dehydroalanine moiety of the NiII complex 1 of a Schiff′s base derived from (S)-o-[N-(N′-benzylprolyl)amino]benzophenone (BPB) and dehydroalanine is described. The radical addition produced a mixture of diastereoisomeric complexes 4a–d with a 40–90% excess of (S,S)diastereoisomers over the (S,R)-ones, giving the reaction products in almost quantitative yields. The diastereoselectivity of the reaction depended on the size of the entering radicals, the most effective asymmetric induction being achieved for the But radical addition. Enantiomerically pure ‘(S)-2-amino3-(tert-butyl)propanoic acid’[(S)-γ-methylleucine] and the chiral auxiliary BPB were recovered from compound 4d after its decomposition with HCl. The reactivities of the carbon–centred radicals towards the carbon-carbon double bond in the amino acid moiety of the complex 1 was quantitatively established by using ESR spectroscopy in the spin-trap technique.