TY - JOUR
T1 - Investigation of Lipase-Catalyzed Michael-type Carbon-Carbon Bond Formations
AU - Strohmeier, G.A.
AU - Sovic, T.
AU - Steinkellner, G.
AU - Hartner, Franz Stefan
AU - Andryushkova, Aleksandra
AU - Purkarthofer, T.
AU - Glieder, Anton
AU - Gruber, K.
AU - Griengl, Herfried
PY - 2009
Y1 - 2009
N2 - Conjugate additions of carbon nucleophiles to appropriate acceptor molecules were investigated with respect to the synthetic potential and stereochemistry of the products. Reactions of short-chain α,β-unsaturated ketones and mono-substituted nitroalkenes with CH-acidic carboxylic ester derivatives were catalyzed by various immobilized lipases. Using methyl nitroacetate complete conversion with methyl vinyl ketone and trans-β-nitrostyrene was obtained. The reactions proceeded without enantioselectivity. Evidence for enzyme catalysis is provided by the observation that after denaturation of Candida antarctica lipase B or inhibition no reaction took place. Docking studies with the chiral addition product methyl 2-methyl-2-nitro-5-oxohexanoate did not reveal any specific binding mode for this reaction product, which would have been the requirement for stereoselective additions. These results support the experimental findings that the conjugate addition takes place without enantiopreference.
AB - Conjugate additions of carbon nucleophiles to appropriate acceptor molecules were investigated with respect to the synthetic potential and stereochemistry of the products. Reactions of short-chain α,β-unsaturated ketones and mono-substituted nitroalkenes with CH-acidic carboxylic ester derivatives were catalyzed by various immobilized lipases. Using methyl nitroacetate complete conversion with methyl vinyl ketone and trans-β-nitrostyrene was obtained. The reactions proceeded without enantioselectivity. Evidence for enzyme catalysis is provided by the observation that after denaturation of Candida antarctica lipase B or inhibition no reaction took place. Docking studies with the chiral addition product methyl 2-methyl-2-nitro-5-oxohexanoate did not reveal any specific binding mode for this reaction product, which would have been the requirement for stereoselective additions. These results support the experimental findings that the conjugate addition takes place without enantiopreference.
U2 - /10.1016/j.tet.2009.05.042
DO - /10.1016/j.tet.2009.05.042
M3 - Article
VL - 65
SP - 5663
EP - 5668
JO - Tetrahedron
JF - Tetrahedron
SN - 0040-4020
IS - 29
ER -