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Sequential Two‐Step Stereoselective Amination of Allylic Alcohols through the Combination of Laccases and Amine Transaminases
Author(s) -
AlbarránVelo Jesús,
Lavandera Iván,
GotorFernández Vicente
Publication year - 2020
Publication title -
chembiochem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.05
H-Index - 126
eISSN - 1439-7633
pISSN - 1439-4227
DOI - 10.1002/cbic.201900473
Subject(s) - chemistry , stereoselectivity , amine gas treating , transamination , amination , enantiomeric excess , reductive amination , transaminase , ketone , combinatorial chemistry , enantiomer , organic chemistry , selectivity , oxidative deamination , biocatalysis , benzylamine , cascade reaction , catalysis , enantioselective synthesis , reaction mechanism , enzyme
A sequential two‐step chemoenzymatic methodology for the stereoselective synthesis of (3 E )‐4‐(het)arylbut‐3‐en‐2‐amines in a highly selective manner and under mild reaction conditions is described. The approach consists of oxidation of the corresponding racemic alcohol precursors by the use of a catalytic system made up of the laccase from Trametes versicolor and the oxy‐radical TEMPO, followed by the asymmetric reductive bio‐transamination of the corresponding ketone intermediates. Optimisation of the oxidation reaction, exhaustive amine transaminase screening for the bio‐transaminations and the compatibility of the two enzymatic reactions were studied in depth in search of a design of a compatible sequential cascade. This synthetic strategy was successful and the combinations of enzymes displayed a broad substrate scope, with 16 chiral amines being obtained in moderate to good isolated yields (29–75 %) and with excellent enantiomeric excess values (94 to >99 %). Interestingly, both amine enantiomers can be achieved, depending on the selectivity of the amine transaminase employed in the system.