Practical two-step synthesis of an enantiopure aliphatic terminal (S)-epoxide based on reduction of haloalkanones with "Designer Cells"

被引：35

作者：

Berkessel, Albrecht ^{[1
]}

Rollmann, Claudia ^{[2
]}

Chamouleau, Francoise ^{[2
]}

Labs, Stefanie ^{[1
]}

May, Oliver ^{[2
]}

Groger, Harald ^{[2
,3
]}

机构：

[1] Univ Cologne, Inst Organ Chem, D-50939 Cologne, Germany

[2] Degussa AG, Serv Ctr Biocatalysis, D-63403 Hanau, Germany

[3] Univ Erlangen Nurnberg, Inst Organ Chem, D-91054 Erlangen, Germany

来源：

ADVANCED SYNTHESIS & CATALYSIS | 2007年 / 349卷 / 17-18期

关键词：

alcohols; asymmetric catalysis; enzyme catalysis; epoxides; halohydrins; reduction;

D O I：

10.1002/adsc.200700244

中图分类号：

O69 [应用化学];

学科分类号：

081704 ;

摘要：

A practical biocatalytic method for the synthesis of aliphatic P-halogenated (S)-alcohols as epoxide precursors by means of an enantioselective reduction of the corresponding ketones with recombinant whole cells, bearing an alcohol dehydrogenase and a glucose dehydrogenase, was developed. The biotransformations operate at high substrate concentrations of up to 208 g/L, and afford the (S)-beta-halohydrins with both high conversions of > 95 % and enantioselectivities of > 99 % ee. Base-induced cyclization of the P-halohydrin intermediates gave the desired (S)-epoxides in high yield and enantiomeric purity (> 99 % ee).

引用

页码：2697 / 2704

页数：8

共 35 条

[21] Construction of pseudo-heterochiral and homochiral di-μ-oxotitanium(Schiff base) dimers and enantioselective epoxidation using aqueous hydrogen peroxide [J].

Matsumoto, K ;

Sawada, Y ;

Saito, B ;

Sakai, K ;

Katsuki, T .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2005, 44 (31) :4935-4939

[22] Microbiological transformations 40. Use of fungal epoxide hydrolases for the synthesis of enantiopure alkyl epoxides [J].

Moussou, P ;

Archelas, A ;

Furstoss, R .

TETRAHEDRON, 1998, 54 (08) :1563-1572

[23] ASYMMETRIC EPOXIDATION OF LONG-CHAIN TERMINAL OLEFINS BY CORYNEBACTERIUM-EQUI-IFO 3730 [J].

OHTA, H ;

TETSUKAWA, H .

AGRICULTURAL AND BIOLOGICAL CHEMISTRY, 1979, 43 (10) :2099-2104

[24] MICROBIAL EPOXIDATION OF LONG-CHAIN TERMINAL OLEFINS [J].

OHTA, H ;

TETSUKAWA, H .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1978, (19) :849-850

[25] Non-racemic halohydrins via biocatalytic hydrogen-transfer reduction of halo-ketones and one-pot cascade reaction to enantiopure epoxides [J].

Poessl, TM ;

Kosjek, B ;

Ellmer, U ;

Gruber, CC ;

Edegger, K ;

Faber, K ;

Hildebrandt, P ;

Bornscheuer, UT ;

Kroutil, W .

ADVANCED SYNTHESIS & CATALYSIS, 2005, 347 (14) :1827-1834

[26] A SYSTEMATIC STUDY ON THE BAKERS-YEAST REDUCTION OF 2-OXOALKYL BENZOATES AND 1-CHLORO-2-ALKANONES [J].

SAKAI, T ;

WADA, K ;

MURAKAMI, T ;

KOHRA, K ;

IMAJO, N ;

OOGA, Y ;

TSUBOI, S ;

TAKEDA, A ;

UTAKA, M .

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 1992, 65 (03) :631-638

[27] A practical method for epoxidation of terminal olefins with 30% hydrogen peroxide under halide-free conditions [J].

Sato, K ;

Aoki, M ;

Ogawa, M ;

Hashimoto, T ;

Noyori, R .

JOURNAL OF ORGANIC CHEMISTRY, 1996, 61 (23) :8310-8311

[28] LIGAND-EXCHANGE REACTION OF SULFOXIDES IN ORGANIC-SYNTHESIS - A NEW SYNTHESIS OF ALPHA-CHLOROKETONES FROM CARBONYL-COMPOUNDS WITH ONE-CARBON HOMOLOGATION [J].

SATOH, T ;

MIZU, Y ;

KAWASHIMA, T ;

YAMAKAWA, K .

TETRAHEDRON, 1995, 51 (03) :703-710

[29] Titanium-salan-catalyzed asymmetric epoxidation with aqueous hydrogen peroxide as the oxidant [J].

Sawada, Yuji ;

Matsumoto, Kazuhiro ;

Kondo, Shoichi ;

Watanabe, Hisayuki ;

Ozawa, Tomoyuki ;

Suzuki, Kenji ;

Saito, Bunnai ;

Katsuki, Tsutomu .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2006, 45 (21) :3478-3480

[30] Stereo-complementary two-step cascades using a two-enzyme system leading to enantiopure epoxides [J].

Seisser, Birgit ;

Lavandera, Ivan ;

Faber, Kurt ;

Spelberg, Jeffrey H. Lutje ;

Kroutil, Wolfgang .

ADVANCED SYNTHESIS & CATALYSIS, 2007, 349 (8-9) :1399-1404

← 1 2 3 4 →