Catalytic Enantioselective Reaction of α‐Aminoacetonitriles Using Chiral Bis(imidazoline) Palladium Catalysts

Abstract

The catalytic enantioselective reaction of diphenylmethylidene-protected α-aminoacetonitriles with imines has been developed. Good yields and diastereo- and enantioselectivities were observed for the reaction of various imines using chiral bis(imidazoline)/Pd catalysts. The reaction of α-aminonitriles with di-tert-butyl azodicarboxylate afforded chiral α,α-diaminonitriles in high yields with high enantioselectivities.

Chiral Imidazoline Ligands and Their Applications in Metal‐Catalyzed Asymmetric Synthesis†

“…The four catalysts were employed in the nucleophilic addition of α ‐cyanocarbanions with imines. Utilizing benzyl nitrile, [ 100 ] acrylonitrile [ 101 ] (via aza‐Morita‐Baylis‐Hillman reaction promoted by DABCO), α ‐cyanoacetic acid [ 102 ] (via decarboxylative cyanoalkylation), α ‐aminoacetonitrile [ 103 ] (using α ‐iminonitriles), α ‐phenylthioacetonitrile, [ 104 ] α , α ‐dichloroacetonitrile [ 105 ] , α , α ‐dithioacetonitrile, [ 106 ] allenylnitrile [ 107 ] as precursors of α ‐cyanocarbanion, different α ‐substituted‐ β ‐aminonitriles could be synthesized (Scheme 47).…”

Recent Advances in the Synthesis of Hydantoins: The State of the Art of a Valuable Scaffold

“…Kondo et al recently developed an enantioselective synthesis of α,β-diaminoacetonitriles, which they used in the Bucherer−Bergs reaction without loss of enantiopurity. 34 Improvements in terms of reaction times, yields, and environmentally friendly conditions were also described. A catalyzed Bucherer−Bergs reaction was reported, in which Fe 3 O 4 nanoparticles were employed as a reusable (up to four times) Lewis acid to promote both the amino nitrile formation and the carbon dioxide addition steps.…”

Synthesis of substituted imid(thi)azolidines by [3+2] cycloaddition of aziridines with nitriles(isothiocyanates) via visible light photocatalysis

“…[10][11] Some derivatives are used for the synthesis of anti-inflammatory, antioxidant, anti-nociceptive and anticarcinogenic drugs. Additionally, imidazolines have been used as metal complex ligands 12 and auxiliary groups 13 in asymmetric synthesis. Many methods have been developed for the synthesis of imidazolines and thiazolines.…”