Highly enantioselective hydrolysis of alicyclic meso-epoxides with a bacterial epoxide hydrolase from Sphingomonas sp. HXN-200: simple syntheses of alicyclic vicinal trans-diols

Chang, Dongliang; Wang, Zunsheng; Heringa, M. F.; Wirthner, Renato; Li, Zhi

doi:10.1039/b300435j

Cited by 39 publications

(27 citation statements)

References 20 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Fore xample,t he epoxide hydrolase HXN-200 catalyzes ring opening and desymmetrization of epoxides fused to 5-and 6-membered rings ( Figure 58). [190] Thed esymmetrization of achiral epoxides represents one of the highlights of asymmetric chemocatalysis.J acobsen has developed ac lass of cobalt-salen complexes that are highly effective for the synthesis of diols. [42a, 191] Significantly this approach has been extended to the use of av ariety of nucleophiles to give rise to other classes of chiral secondary alcohols.…”

Section: Epoxide Opening With Oxygen Nucleophilesmentioning

confidence: 99%

“…Epoxide hydrolases mediate ring opening of epoxides to yield diols (Figure ). For example, the epoxide hydrolase HXN‐200 catalyzes ring opening and desymmetrization of epoxides fused to 5‐ and 6‐membered rings (Figure ) . The desymmetrization of achiral epoxides represents one of the highlights of asymmetric chemocatalysis.…”

Section: Hydrolysis and Condensation Reactionsmentioning

confidence: 99%

See 1 more Smart Citation

Enantioselective Chemo‐ and Biocatalysis: Partners in Retrosynthesis

et al. 2017

View full text Add to dashboard Cite

Recent developments of stereoselective biocatalytic and chemocatalytic methods are discussed. The review provides a guide to the use of biocatalytic methods in the area of chemical synthesis with focused attention on retrosynthetic considerations and analysis. The transformations presented are organized according to bond disconnections and attendant synthetic methods. The review is expected to lead to better understanding of the characteristics and distinctions of the two complementary approaches. It depicts for researchers in bio- and chemocatalysis a road map of challenges and opportunities for the evolution (and at times revolution) in chemical synthesis.

show abstract

Section: Epoxide Opening With Oxygen Nucleophilesmentioning

confidence: 99%

Section: Hydrolysis and Condensation Reactionsmentioning

confidence: 99%

Enantioselective Chemo‐ and Biocatalysis: Partners in Retrosynthesis

et al. 2017

View full text Add to dashboard Cite

show abstract

“…Initially only the yeast R. glutinis was successful at enantioselective hydrolysis of cyclohexene and cyclopentene oxide affording the (R,R)-diols (90 and 98 % ee respectively) [58]. However, recently a Sphingomonas strain converted N-benzyloxycarbonyl-3,4-epoxy-pyrrolidine and cyclohexene oxide to the corresponding (R,R)-diols with respectively 95 and 86 % ee [59].…”

Section: Type Iv: Alkyl 23-disubstituted Epoxidesmentioning

confidence: 98%

Diversity of Epoxide Hydrolase Biocatalysts

Labuschagne¹

2006

COC

View full text Add to dashboard Cite

Chiral epoxides and their derivatives are versatile intermediates for the synthesis of enantiopure organic chemicals. Chiral epoxides can be obtained through asymmetric epoxidation using either chemical catalysts or epoxidizing enzymes such as monooxygenases or chloroperoxidases. Alternatively hydrolytic kinetic resolution of racemic epoxides can yield a mixture containing, in an ideal situation, a single enantiomer of the remaining epoxide and a single enantiomer of the formed diol. Occasionally catalysts with complementary enantioselectivities and opposite regioselectivities can give through enantioconvergent hydrolysis one diol enantiomer in > 90% yield. Hydrolyses can also be performed with either metal catalysts or biological catalysts, mainly epoxide hydrolases. Epoxide hydrolases show great promise for the preparative scale hydrolysis of epoxides, because they are easy-to-use biocatalysts that accept a wide range of substrates, that do not require co-factors and that show improved activity when the substrate is present as a second water immiscible phase. X-ray structures for one fungal, one bacterial and two mammalian epoxide hydrolases are available as well as gene sequences for more than ninety five epoxide hydrolases. Expression systems in Escherichia coli and other hosts have also been developed and different assays suitable for high throughput screening have been developed and tested. The latter developments also made possible the first attempts at catalyst improvement through site directed mutagenesis and directed evolution. This review will give a comparative overview of the different types of epoxide hydrolases, which recently gave promising results for hydrolytic kinetic or enantioconvergent resolution of different types of epoxides and of results obtained with various recombinant epoxide hydrolases.

show abstract

“…55,56 The asymmetrized trans-diol (3R,4R)-44 was recovered with high optical purity and isolated yield. On the other hand, moderate stereoselectivity was observed in the enzymatic trans-hydrolysis of (()-cis-48.…”

Section: Heterocyclic Amides and Carbamatesmentioning

confidence: 99%