Asymmetric bioreduction of C=C bonds using enoate reductases OPR1, OPR3 and YqjM: Enzyme-based stereocontrol

被引：151

作者：

Hall, Melanie ^{[1
]}

Stueckler, Clemens ^{[1
]}

Ehammer, Heidemarie ^{[2
]}

Pointner, Eva ^{[2
]}

Oberdorfer, Gustav ^{[3
]}

Gruber, Karl ^{[3
]}

Hauer, Bernard ^{[4
]}

Stuermer, Rainer ^{[4
]}

Kroutil, Wolfgang ^{[1
]}

Macheroux, Peter ^{[2
]}

Faber, Kurt ^{[1
]}

机构：

[1] Graz Univ, Dept Organ Chem & Bioorgan Chem, A-8010 Graz, Austria

[2] Graz Univ Technol, Inst Biochem, A-8010 Graz, Austria

[3] Graz Univ, Dept Chem Struct Biol, A-8010 Graz, Austria

[4] BASF AG, GVF E B9, D-67056 Ludwigshafen, Germany

来源：

ADVANCED SYNTHESIS & CATALYSIS | 2008年 / 350卷 / 03期

关键词：

asymmetric bioreduction; enoate reductase; nitroalkenes; old yellow enzyme; stereocomplementary process; alpha; beta-unsaturated carbonyl compounds; OLD YELLOW ENZYME; TRANSFER HYDROGENATION; CRYSTAL-STRUCTURE; REDUCTION; ENANTIOSELECTIVITY; RESOLUTION; MECHANISM; CATALYSIS; COMPOUND; BINDING;

D O I：

10.1002/adsc.200700458

中图分类号：

O69 [应用化学];

学科分类号：

081704 ;

摘要：

Three cloned enoate, reductases from the "old yellow enzyme" family of flavoproteins were investigated in the asymmetric bioreduction of activated alkenes. 12-Oxophytodienoate reductase isoenzymes OPR1 and OPR3 from Lycopersicon esculentum (tomato), and YqjM from Bacillus subtilis displayed a remarkably broad substrate spectrum by reducing a,p-unsaturated aldehydes, ketones, maleimides and nitroalkenes. The reaction proceeded with absolute chemoselectivity - only the conjugated C=C bond was reduced, while isolated olefins and carbonyl groups remained intact - with excellent stereoselectivities (ees up to > 99%). Upon reduction of a nitroalkene, the stereochemical outcome could be determined via choice of the appropriate enzyme (OPR1 versus OPR3 or YqjM), which furnished the corresponding enantiomeric nitroalkanes in excellent ee. Molecular modelling suggests that this "enzyme-based stereocontrol" is caused by subtle differences within the active site geometries.

引用

页码：411 / 418

页数：8

共 65 条

[11] Microbial oxidation of amines:: A preliminary investigation on the resolution of racemic 1-phenylethyl amine [J].

Ferré, E ;

N'guyen, MH ;

Le Petit, J ;

Gil, G .

BIOCATALYSIS AND BIOTRANSFORMATION, 2002, 20 (05) :311-317

[12] EFFICIENT STEREOSELECTIVE SYNTHESIS OF NATURAL ALPHA-TOCOPHEROL (VITAMIN-E) [J].

FUGANTI, C ;

GRASSELLI, P .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1979, (22) :995-997

[13] BAKERS-YEAST MEDIATED SYNTHESIS OF NATURAL-PRODUCTS [J].

FUGANTI, C .

PURE AND APPLIED CHEMISTRY, 1990, 62 (07) :1449-1452

[14]

Gatfield I.L., 1997, Advances in Biochemical Engineering/Biotechnology, V55, P221

[15]

HALL M, 2007, ANGEW CHEM, V119, P4006

[16] Asymmetric bioreduction of activated alkenes using cloned 12-oxophytodienoate reductase isoenzymes OPR-1 and OPR-3 from Lycopersicon esculentum (Tomato):: A striking change of stereoselectivity [J].

Hall, Melanie ;

Stueckler, Clemens ;

Kroutil, Wolfgang ;

Macheroux, Peter ;

Faber, Kurt .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2007, 46 (21) :3934-3937

[17] Asymmetric whole-cell bioreduction of an α,β-unsaturated aldehyde (citral):: competing prim-alcohol dehydrogenase and C-C lyase activities [J].

Hall, Melanie ;

Hauer, Bernhard ;

Stuermer, Rainer ;

Kroutil, Wolfgang ;

Faber, Kurt .

TETRAHEDRON-ASYMMETRY, 2006, 17 (21) :3058-3062

[18] Hydrogenation of the C-C double bond of maleimides with cultured plant cells [J].

Hirata, T ;

Takarada, A ;

Hegazy, MEF ;

Sato, Y ;

Matsushima, A ;

Kondo, Y ;

Matsuki, A ;

Hamada, H .

JOURNAL OF MOLECULAR CATALYSIS B-ENZYMATIC, 2005, 32 (04) :131-134

[19] Enzyme promiscuity: mechanism and applications [J].

Hult, Karl ;

Berglund, Per .

TRENDS IN BIOTECHNOLOGY, 2007, 25 (05) :231-238

[20] Inversion of enantioselectivity of asymmetric biocatalytic decarboxylation by site-directed mutagenesis based on the reaction mechanism [J].

Ijima, Y ;

Matoishi, K ;

Terao, Y ;

Doi, N ;

Yanagawa, H ;

Ohta, H .

CHEMICAL COMMUNICATIONS, 2005, (07) :877-879

← 1 2 3 4 5 6 7 →