Asymmetric total synthesis of (+)-exo-brevicomin based on enantioconvergent biocatalytic hydrolysis of an alkene-functionalized 2,3-disubstituted epoxide

2002 ◽  
Vol 80 (4) ◽  
pp. 362-369 ◽  
Author(s):  
Sandra F Mayer ◽  
Harald Mang ◽  
Andreas Steinreiber ◽  
Robert Saf ◽  
Kurt Faber
Keyword(s):  
Total Synthesis ◽  
Asymmetric Synthesis ◽  
Bark Beetle ◽  
Epoxide Hydrolase ◽  
Beetle Species ◽  
Asymmetric Total Synthesis ◽  
Epoxide Hydrolases ◽  
Pheromone System ◽  
Enantioconvergent Hydrolysis ◽  
Hydrolysis Of

A short total asymmetric synthesis of (+)-exo- and (–)-endo-brevicomin ((+)-exo-3 and (–)-endo-3), which are components of the attracting pheromone system of several bark-beetle species belonging to the genera Dendroctonus and Dryocoetes, was accomplished via a chemoenzymatic protocol. The key step consisted of biocatalytic hydrolysis by bacterial epoxide hydrolases of cis-configured 2,3-disubstituted oxiranes bearing olefinic side chains. This reaction proceeded in an enantioconvergent fashion, by affording a single enantiomeric vic-diol from the rac-epoxide in up to 92% ee and 83% isolated yield.Key words: bacterial epoxide hydrolase, 2,3-disubstituted oxirane, enantioconvergent hydrolysis, (+)-exo-brevicomin, (–)-endo-brevicomin.

Previously published / Prédémment paruAsymmetric total synthesis of (+)-exo-brevicomin based on enantioconvergent biocatalytic hydrolysis of an alkene-functionalized 2,3-disubstituted epoxide

2002 ◽  
Vol 80 (6) ◽  
Author(s):  
Sandra F Mayer ◽  
Harald Mang ◽  
Andreas Steinreiber ◽  
Robert Saf ◽  
Kurt Faber
Keyword(s):  
Total Synthesis ◽  
Asymmetric Synthesis ◽  
Bark Beetle ◽  
Epoxide Hydrolase ◽  
Side Chains ◽  
Beetle Species ◽  
Epoxide Hydrolases ◽  
Pheromone System ◽  
Enantioconvergent Hydrolysis ◽  
Hydrolysis Of

A short total asymmetric synthesis of (+)-exo- and (–)-endo-brevicomin ((+)-exo-3 and (–)-endo-3), which are components of the attracting pheromone system of several bark-beetle species belonging to the genera Dendroctonus and Dryocoetes, was accomplished via a chemoenzymatic protocol. The key step consisted of biocatalytic hydrolysis by bacterial epoxide hydrolases of cis-configured 2,3-disubstituted oxiranes bearing olefinic side chains. This reaction proceeded in an enantioconvergent fashion, by affording a single enantiomeric vic-diol from the rac-epoxide in up to 92% ee and 83% isolated yield.Key words: bacterial epoxide hydrolase, 2,3-disubstituted oxirane, enantioconvergent hydrolysis, (+)-exo-brevicomin, (–)-endo-brevicomin.

Asymmetric total synthesis of (−)-δ-lycorane

2017 ◽  
Vol 4 (6) ◽  
pp. 1149-1152 ◽  
Author(s):  
Junliang Wang ◽  
Jianneng Li ◽  
Xianwang Shen ◽  
Cong Dong ◽  
Jun Lin ◽  
...  
Keyword(s):  
Total Synthesis ◽  
Asymmetric Synthesis ◽  
Cascade Reaction ◽  
Asymmetric Total Synthesis

A first asymmetric synthesis of (−)-δ-lycorane by using a chiral bifunctional squaramide-catalysed cascade reaction is reported.

ChemInform Abstract: The Asymmetric Synthesis of Fused Cyclopentenone Ring Systems: A Formal Asymmetric Total Synthesis of (-)-Isocomene.

ChemInform ◽  
2010 ◽  
Vol 27 (37) ◽  
pp. no-no
Author(s):  
A. I. MEYERS ◽  
S. BIENZ ◽  
H.-B. KWON ◽  
R. H. WALLACE
Keyword(s):  
Total Synthesis ◽  
Asymmetric Synthesis ◽  
Asymmetric Total Synthesis ◽  
Ring Systems

Enantioconvergent Hydrolysis of Styrene Epoxides by Newly Discovered Epoxide Hydrolases in Mung Bean

2006 ◽  
Vol 8 (8) ◽  
pp. 1737-1740 ◽  
Author(s):  
Wei Xu ◽  
Jian-He Xu ◽  
Jiang Pan ◽  
Qing Gu ◽  
Xin-Yan Wu
Keyword(s):  
Mung Bean ◽  
Epoxide Hydrolases ◽  
Enantioconvergent Hydrolysis ◽  
Hydrolysis Of

Asymmetric synthesis of machilin C and its analogue

2010 ◽  
Vol 64 (5) ◽  
Author(s):  
Yamu Xia ◽  
Wei Wang
Keyword(s):  
Total Synthesis ◽  
Asymmetric Synthesis ◽  
Absolute Configuration ◽  
Asymmetric Induction ◽  
Mitsunobu Reaction ◽  
Asymmetric Total Synthesis ◽  
Twelve Steps ◽  
The Absolute

AbstractFull details of the asymmetric total synthesis of erythro-8-O-4′-neolignan, machilin C, and its analogue perseal A are reported. The synthesis was involved in the Sharpless dihydroxylation reaction that occurred with excellent asymmetric induction, and the Mitsunobu reaction which occurred with inversion of the absolute configuration from the threo to the erythro isomer. The synthesis was achieved from simple vanillin in eight to twelve steps.

A concise asymmetric synthesis of (−)-trans-aerangis lactone

2018 ◽  
Vol 96 (12) ◽  
pp. 1061-1063 ◽  
Author(s):  
Rachana Pandey ◽  
Ranjana Prakash
Keyword(s):  
Ethylene Glycol ◽  
Total Synthesis ◽  
Asymmetric Synthesis ◽  
Aldol Reaction ◽  
Starting Material ◽  
Asymmetric Total Synthesis

A concise stereoselective approach to functionalized δ-lactone skeleton from monosilylated ethylene glycol as a starting material and its application to the asymmetric total synthesis of (−)-trans-aerangis lactone have been demonstrated. The synthesis utilizes the organocatalyzed MacMillan’s cross aldol reaction as a key step.

Asymmetric total synthesis of cephanolide B

2021 ◽  
Author(s):  
Hongyuan Zhang ◽  
Haibing He ◽  
Shuanhu Gao
Keyword(s):  
Total Synthesis ◽  
Asymmetric Synthesis ◽  
Asymmetric Total Synthesis ◽  
First Time

The asymmetric synthesis of cephanolide B, a complex C18 Cephalotaxus dinorditerpenoid, is presented for the first time.

scholarly journals Substantially improving the enantioconvergence of PvEH1, a Phaseolus vulgaris epoxide hydrolase, towards m-chlorostyrene oxide by laboratory evolution

2019 ◽  
Vol 18 (1) ◽  
Author(s):  
Xun-Cheng Zong ◽  
Chuang Li ◽  
Yao-Hui Xu ◽  
Die Hu ◽  
Bo-Chun Hu ◽  
...  
Keyword(s):  
Phaseolus Vulgaris ◽  
Epoxide Hydrolase ◽  
Substrate Binding ◽  
Binding Pocket ◽  
Saturation Mutagenesis ◽  
Substrate Binding Pocket ◽  
Laboratory Evolution ◽  
E Coli ◽  
Enantioconvergent Hydrolysis ◽  
Hydrolysis Of

Abstract Background Epoxide hydrolase can regioselectively catalyze the oxirane ring-opening hydrolysis of rac-epoxides producing the corresponding chiral diols. In our laboratory, a gene named pveh1 encoding an EH from Phaseolus vulgaris was cloned. Although the directed modification of PvEH1 was carried out, the mutant PvEH1Y3 showed a limited degree of enantioconvergence towards racemic (rac-) m-chlorostyrene oxide (mCSO). Results PvEH1 and PvEH1Y3 were combinatively subjected to laboratory evolution to further enhance the enantioconvergence of PvEH1Y3 towards rac-mCSO. Firstly, the substrate-binding pocket of PvEH1 was identified using a CAVER 3.0 software, and divided into three zones. After all residues in zones 1 and 3 were subjected to leucine scanning, two E. coli transformants, E. coli/pveh1Y149L and /pveh1P184L, were selected, by which rac-mCSO was transformed into (R)-m-chlorophenyl-1,2-ethanediol (mCPED) having 55.1% and 27.2% eep. Secondly, two saturation mutagenesis libraries, E. coli/pveh1Y149X and /pveh1P184X (X: any one of 20 residues) were created at sites Y149 and P184 of PvEH1. Among all transformants, both E. coli/pveh1Y149L (65.8% αS and 55.1% eep) and /pveh1P184W (66.6% αS and 59.8% eep) possessed the highest enantioconvergences. Finally, the combinatorial mutagenesis was conducted by replacements of both Y149L and P184W in PvEH1Y3, constructing E. coli/pveh1Y3Z2, whose αS reached 97.5%, higher than that (75.3%) of E. coli/pveh1Y3. In addition, the enantioconvergent hydrolysis of 20 mM rac-mCSO was performed by E. coli/pveh1Y3Z2, giving (R)-mCPED with 95.2% eep and 97.2% yield. Conclusions In summary, the enantioconvergence of PvEH1Y3Z2 was successfully improved by laboratory evolution, which was based on the study of substrate-binding pocket by leucine scanning. Our present work introduced an effective strategy for the directed modification of enantioconvergence of PvEH1.

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