74669-69-5Relevant academic research and scientific papers
Synthesis of Chiral Amines via a Bi-Enzymatic Cascade Using an Ene-Reductase and Amine Dehydrogenase
Jongkind, Ewald P. J.,Fossey-Jouenne, Aurélie,Mayol, Ombeline,Zaparucha, Anne,Vergne-Vaxelaire, Carine,Paul, Caroline E.
, (2021/12/23)
Access to chiral amines with more than one stereocentre remains challenging, although an increasing number of methods are emerging. Here we developed a proof-of-concept bi-enzymatic cascade, consisting of an ene reductase and amine dehydrogenase (AmDH), to afford chiral diastereomerically enriched amines in one pot. The asymmetric reduction of unsaturated ketones and aldehydes by ene reductases from the Old Yellow Enzyme family (OYE) was adapted to reaction conditions for the reductive amination by amine dehydrogenases. By studying the substrate profiles of both reported biocatalysts, thirteen unsaturated carbonyl substrates were assayed against the best duo OYE/AmDH. Low (5 %) to high (97 %) conversion rates were obtained with enantiomeric and diastereomeric excess of up to 99 %. We expect our established bi-enzymatic cascade to allow access to chiral amines with both high enantiomeric and diastereomeric excess from varying alkene substrates depending on the combination of enzymes.
Stereochemistry of Aliphatic Carbocations, 14. Alkyl Shifts from Secondary to Primary Carbon Atoms
Kirmse, Wolfgang,Guenther, Bernd-Rainer,Knist, Johannes,Kratz, Sigrid,Loosen, Karin,et al.
, p. 2127 - 2139 (2007/10/02)
Alkyl shifts from secondary to primary carbon atoms have been induced by the nitrous acid deamination of suitable amines (4, 22, 39, 51); they include sequential rearrangements (-CH3,CH3 and -CH3,H).Predominant although incomplete inversion at the migration origin has been observed (Me 70percent, Et 62-64percent, nPr 65percent, iPr 64percent, tBu 55percent).Our results require the intervention of open secondary carbocations which may be preceded by less stable bridged intermediates.
