Biocatalytic kinetic resolution of racemic hydroperoxides through the enantioselective reduction with free and immobilized microorganisms

被引:12
作者
Adam, W
Lukacs, Z
Saha-Möller, CR
Schreier, P
机构
[1] Univ Wurzburg, Inst Organ Chem, D-97074 Wurzburg, Germany
[2] Univ Wurzburg, Inst Food Chem, D-97074 Wurzburg, Germany
关键词
D O I
10.1021/ja994530a
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A Bacillus subtilis strain, isolated from topsoil by a selective screening procedure, is effective for the biocatalytic kinetic resolution of racemic hydroperoxides: A variety of secondary aralkyl hydroperoxides have been resolved by this microorganism in moderate to high enantioselectivities [up to 88% ee for the (R)-hydroperoxide]. This topsoil bacterium B. subtilis also reduced the racemic tertiary 1-methyl-(1-phenyl)propyl hydroperoxide enantioselectively to afford the (R)-hydroperoxide in 39% ee. In contrast to the bacteria, the fungus Aspergillus niger displayed the reverse sense of enantioselectivity in the kinetic resolution of the racemic hydroperoxides, that is, the (R) enantiomer was preferably reduced and the (S)-hydroperoxide was obtained in enantiomerically enriched form. Such an inverse enantioselectivity has not been observed before for the peroxidases of bacterial versus fungal and plant sources. Furthermore, it was shown that immobilized B. subtilis cells may be reused for several catalytic cycles in the kinetic resolution of racemic hydroperoxides without any loss of enzymatic activity. This microbial process offers a promising biocatalytic methodology for the preparation of optically active hydroperoxides.
引用
收藏
页码:4887 / 4892
页数:6
相关论文
共 30 条
[1]  
Adam W, 1999, Adv Biochem Eng Biotechnol, V63, P73
[2]   Titanium-catalyzed, asymmetric sulfoxidation of alkyl aryl sulfides with optically active hydroperoxides [J].
Adam, W ;
Korb, MN ;
Roschmann, KJ ;
Saha-Möller, CR .
JOURNAL OF ORGANIC CHEMISTRY, 1998, 63 (10) :3423-3428
[3]   Biotransformation of (1-phenyl)ethyl hydroperoxide with Aspergillus niger:: a model study on enzyme selectivity and on the induction of peroxidase activity [J].
Adam, W ;
Lukacs, Z ;
Saha-Möller, CR ;
Schreier, P .
BIOCHIMICA ET BIOPHYSICA ACTA-GENERAL SUBJECTS, 1999, 1427 (02) :236-244
[4]   METAL-CATALYZED DIRECT HYDROXY-EPOXIDATION OF OLEFINS [J].
ADAM, W ;
RICHTER, MJ .
ACCOUNTS OF CHEMICAL RESEARCH, 1994, 27 (02) :57-62
[5]   Asymmetric synthesis with the enzyme Coprinus peroxidase:: Kinetic resolution of chiral hydroperoxides and enantioselective sulfoxidation [J].
Adam, W ;
Mock-Knoblauch, C ;
Saha-Möller, CR .
JOURNAL OF ORGANIC CHEMISTRY, 1999, 64 (13) :4834-4839
[6]   The titanium-catalyzed, asymmetric epoxidation of allylic alcohols with optically active hydroperoxides in the presence of achiral diol ligands [J].
Adam, W ;
Korb, MN .
TETRAHEDRON-ASYMMETRY, 1997, 8 (07) :1131-1142
[7]   ENZYME-CATALYZED ASYMMETRIC-SYNTHESIS - KINETIC RESOLUTION OF RACEMIC HYDROPEROXIDES BY ENANTIOSELECTIVE REDUCTION TO ALCOHOLS WITH HORSERADISH-PEROXIDASE [J].
ADAM, W ;
HOCH, U ;
LAZARUS, M ;
SAHAMOLLER, CR ;
SCHREIER, P .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (48) :11898-11901
[8]   Microscale determination of the absolute configuration of α-aryl-substituted alcohols by the CD exciton chirality method [J].
Adam, W ;
Lukacs, Z ;
Viebach, K ;
Humpf, HU ;
Saha-Möller, CR ;
Schreier, P .
JOURNAL OF ORGANIC CHEMISTRY, 2000, 65 (01) :186-190
[9]   Kinetic resolution of chiral hydroperoxides:: Hydrogen-peroxide-mediated screening of peroxidase-active soil bacteria [J].
Adam, W ;
Boss, B ;
Harmsen, D ;
Lukacs, Z ;
Saha-Möller, CR ;
Schreier, P .
JOURNAL OF ORGANIC CHEMISTRY, 1998, 63 (22) :7598-7599
[10]  
ADAM W, 1996, J CHEM SOC CHEM COMM, P2701