Enantiodivergence in the reduction of α-methyl and α-halomethyl enones by microorganisms

Abstract Enones ( Z )-3-methyl-( Z )-3-chloromethyl- and ( Z )-3-bromomethyl-4-R-3-buten-2-one (R =  n -pentyl, phenyl, 2′- and 4′-chlorophenyl, 3′- and 4′-nitrophenyl, 4′-methoxyphenyl) were synthesized and subjected to reduction by the microorganisms Saccharomyces cerevisiae and Geotrichum candidum . Whereas the bioreduction of 3-methy-4-R-3-buten-2-ones afforded the corresponding ( S )-4-R-3-methybutan-2-ones, the bioreduction of 3-chloromethyl- and 3-bromomethyl-4-R-3-buten-2-ones afforded the corresponding ( R )-4-R-3-methybutan-2-ones.