• 생약학회지
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• 제17권1호
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• pp.67-72
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• 1986

A stereospecific synthesis of 3-methyl-5-(1-hydroxy-4-oxo-2,6,6-trimethyl-2-cyclohexen-1-yl)-cis, trans-2,4-pentadienoic acid (abscisic acid) from ${\alpha}-ionone$ has been investigated. Ethyl 5-(2,6,6-trimetyl-2-cyclohexen-1-yl)-trans-4-penten-2-ynoate $({\alpha},{\beta}-acetylenic\;ester)$, which was synthesized from alpha-ionone in two steps, was stereospecifically converted in good yield into ethyl 3-methyl-5-(2,6,6-trimethyl-2-cyclohexen-1-yl)-cis, trans-2, 4-pentadienoate $({\alpha}-ionylideneacetate)$ by the conjugate addition of lithium dimethylcuprate at $-78^{\circ}C$. Basic hydrolysis of the ethyl ${\alpha}-ionylideneacetate$ gave an abscisic acid precursor, 3-methyl-5-(2,6,6-trimethyl-2-cyclohexen-1-yl)-cis, trans-2,4-pentadienoic acid, which can be oxidized to yield abscisic acid.

• Biotechnology and Bioprocess Engineering:BBE
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• 제7권3호
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• pp.130-137
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• 2002

Microbial lactonohydrolases (intramolecular ester bond-hydrolyzing enzymes) with unique properties were found. The lactonohydrolase from Fusarium oxysporum catalyzes enantiose-lective hydrolysis of aldonate lactones and D-pantoyl lactone (D-PL). This enzyme is useful for the large-scale optical resolution of racemic PL. The Agrobacterium tumefaciens enzyme catalyzes asymmetric hydrolysis of PL, but the stereospecificity is opposite to that of the Fusarium enzyme. Dihydrocoumarin hydrolase (DHase) from Acinetobacter calcoaceticus is a bifunctional enzyme, which catalyzes not only hydrolysis of aromatic lactones but also bromination of monochlorodi-medon in the presence of H$_2$O$_2$and dihydrocoumarin. DHase also hydrolyzes several linear esters, and is useful for enantioselective hydrolysis of methyl DL-$\beta$-acetylthioisobutyrate and regioselective hydrolysis of methyl cetraxate.

• Archives of Pharmacal Research
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• 제9권1호
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• pp.45-47
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• 1986

Phenylglycine was obtained as the sole metabolite when .alpha.-aminophenylacetonitrile was ted to the culture broth of Aspergillus furmigatus furmigatus. The isolated phenylglycine showed L-configuration with 80% optical purity. Examination of the hydrolysis of the substrate to phenylglycine with cell free extracts, and the supernatant fraction and the particulate fraction both of which were obtained after ultracentrifugation of the cell free extract at 100,000g, indicated that the nitrile group hydrolyzing enzymes, nitrilase existed not only in cytoplasm, but in microsome fractions.

• Current Research on Agriculture and Life Sciences
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• 제5권
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• pp.168-172
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• 1987

광학성체인 isopropylidene glycerols로 부터 mercaptogiycerol을 합성하였다. 1,2-Isopropylideneglycerol을 tosyl화 하고 다시 tosyl group을 thiolacetate로 치환하였다. 염기성 가수분해와 산화에 의해 1,1'-dithiobis-2,3-isopropylidene-2,3-propanediol이 생성되었다. 이 화합물을 mercaptogiycerol 합성을 위해 사용함으로써 1-decenyl lithium으로 cis-S-dec-1'-enyl-2,3-isopropylidene-1-mercapto-2,3-propanediol을 생성하였다. 본 생성물은 plasmalogenase용 thioplasmaloger 기질 조제에 사용된다.

• KSBB Journal
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• 제14권3호
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• pp.291-296
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• 1999

광학활성 에폭사이드는 광학활성 의약품, 농약, 기능성 식품 제조용 핵심 유기중간체로 사용될 수 있다. 광학활성 에폭사이드의 생물공학적 생산 사례로는 diltiazem 합성용 중간체인 methyl trans-3-(4-methoxyphenyl)glycidate를 lipase를 고정화한 중공사막 반응기를 이용하여 생산되고 있으며, 미생물 탈할로겐화반응을 이용하여 광학활성 epichlorohydrin 및 glycidol도 생산되고 있다. 생물공학적으로 광학활성 에폭사이드를 생산하는 방법은 크게 두 가지로 구분할 수 있는데, 알켄 등을 기질로 하여 monooxygenase나 perocidase 등을 이용하여 직접 에폭시화반응을 시키는 방법과 박테리아, 곰팡이, 효모 유래의 미생물 에폭사이드 가수분해효소를 이용하여 라세믹 에폭사이드를 광학분할시켜 얻는 방법이 있다. 특히 에폭사이드 가수분해효소를 이용한 광학활성 에폭사이드 생산은 높은 광학순도를 얻을 수 있으며 일반적으로 라세믹 에폭사이드를 값싸고 쉽게 구할 수 있어 상업화 가능성이 우수하므로 이에 대한 많은 연구개발이 필요하다.

• 한국응용과학기술학회지
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• 제18권3호
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• pp.214-232
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• 2001

CTA ester bonds in TG molecules were not attacked by pancreatic lipase and lipases produced by microbes such as Candida cylindracea, Chromobacterium viscosum, Geotricum candidium, Pseudomonas fluorescens, Rhizophus delemar, R. arrhizus and Mucor miehei. An aliquot of total TG of all the seed oils and each TG fraction of the oils collected from HPLC runs were deuterated prior to partial hydrolysis with Grignard reagent, because CTA molecule was destroyed with treatment of Grignard reagent. Deuterated TG (dTG) was hydrolyzed partially to a mixture of deuterated diacylglycerols (dDG), which were subsequently reacted with (S)-(+)-1-(1-naphthyl)ethyl isocyanate to derivatize into dDG-NEUs. Purified dDG-NEUs were resolved into 1, 3-, 1, 2- and 2, 3-dDG-NEU on silica columns in tandem of HPLC using a solvent of 0.4% propan-1-o1 (containing 2% water)-hexane. An aliquot of each dDG-NEU fraction was hydrolyzed and (fatty acid-PFB ester). These derivatives showed a diagnostic carboxylate ion, $(M-1)^{-}$, as parent peak and a minor peak at m/z 196 $(PFB-CH_{3})^{-}$ on NICI mass spectra. In the mass spectra of the fatty acid-PFB esters of dTGs derived from the seed oils of T. kilirowii and M. charantia, peaks at m/z 285, 287, 289 and 317 were observed, which corresponded to $(M-1)^{-}$ of deuterized oleic acid ($d_{2}-C_{18:0}$), linoleic acid ($d_{4}-C_{18:0}$), punicic acid ($d_{6}-C_{18:0}$) and eicosamonoenoic acid ($d_{2}-C_{20:0}$), respectively. Fatty acid compositions of deuterized total TG of each oil measured by relative intensities of $(M-1)^-$ ion peaks were similar with those of intact TG of the oils by GLC. The composition of fatty acid-PFB esters of total dTG derived from the seed oils of T. kilirowii are as follows; $C_{16:0}$, 4.6 mole % (4.8 mole %, intact TG by GLC), $C_{18:0}$, 3.0 mole % (3.1 mole %), $d_{2}C_{18:0}$, 11.9 mole % (12.5 mole %, sum of $C_{18:1{\omega}9}$ and $C_{18:1{\omega}7}$), $d_{4}-C_{18:0}$, 39.3 mole % (38.9 mole %, sum of $C_{18:2{\omega}6}$ and its isomer), $d_{6}-C_{18:0}$, 41.1 mole % (40.5 mole %, sum of $C_{18:3\;9c,11t,13c}$, $C_{18:3\;9c,11t,13r}$ and $C_{18:3\;9t,11t,13c}$), $d_{2}-C_{20:0}$, 0.1 mole % (0.2 mole % of $C_{20:1{\omega}9}$). In total dTG derived from the seed oils of M. charantia, the fatty acid components are $C_{16:0}$, 1.5 mole % (1.8 mole %, intact TG by GLC), $C_{18:0}$, 12.0 mole % (12.3 mole %), $d_{2}-C_{18:0}$, 16.9 mole % (17.4 mole %, sum of $C_{18:1{\omega}9}$), $d_{4}-C_{18:0}$, 11.0 mole % (10.6 mole %, sum of $C_{18:2{\omega}6}$), $d_{6}-C_{18:0}$, 58.6 mole % (57.5 mole %, sum of $C_{18:3\;9c,11t,13t}$ and $C_{18:3\;9c,11t,13c}$). In the case of Aleurites fordii, $C_{16:0}$; 2.2 mole % (2.4 mole %, intact TG by GLC), $C_{18:0}$; 1.7 mole % (1.7 mole %), $d_{2}-C_{18:0}$; 5.5 mole % (5.4 mole %, sum of $C_{18:1{\omega}9}$), $d_{4}-C_{18:0}$ ; 8.3 mole % (8.5 mole %, sum of $C_{18:2{\omega}6}$), $d_{6}-C_{18:0}$; 82.0 mole % (81.2 mole %, sum of $C_{18:3\;9c,11t,13t}$ and $C_{18:3 9c,11t,13c})$. In the stereospecific analysis of fatty acid distribution in the TG species of the seed oils of T. kilirowii, $C_{18:3\;9c,11t,13r}$ and $C_{18:2{\omega}6}$ were mainly located at sn-2 and sn-3 position, while saturated acids were usually present at sn-1 position. And the major molecular species of $(C_{18:2{\omega}6})(C_{18:3\;9c,11t,13c})_{2}$ and $(C_{18:1{\omega}9})(C_{18:2{\omega}6})(C_{18:3\;9c,11t,13c})$ were predominantly composed of the stereoisomer of $sn-1-C_{18:2{\omega}6}$, $sn-2-C_{18:3\;9c,11t,13c}$, $sn-3-C_{18:3\;9c,11t,13c}$, and $sn-1-C_{18:1{\omega}9}$, $sn-2-C_{18:2{\omega}6}$, $sn-3-C_{18:3\;9c,11t,13c}$, respectively, and the minor TG species of $(C_{18:2{\omega}6})_{2}(C_{18:3\;9c,11t,13c})$ and $ (C_{16:0})(C_{18:3\;9c,11t,13c})_{2}$ mainly comprised the stereoisomer of $sn-1-C_{18:2{\omega}6}$, $sn-2-C_{18:2{\omega}6}$, $sn-3-C_{18:3\;9c,11t,13c}$ and $sn-1-C_{16:0}$, $sn-2-C_{18:3\;9c,11t,13c}$, $sn-3-C_{18:3\;9c,11t,13c}$. The TG of the seed oils of Momordica charantia showed that most of CTA, $C_{18:3\;9c,11t,13r}$, occurred at sn-3 position, and $C_{18:2{\omega}6}$ was concentrated at sn-1 and sn-2 compared to sn-3. Main TG species of $(C_{18:1{\omega}9})(C_{18:3\;9c,11t,13t})_{2}$ and $(C_{18:0})(C_{18:3\;9c,11t,13t})_{2}$ were consisted of the stereoisomer of $sn-1-C_{18:1{\omega}9}$, $sn-2-C_{18:3\;9c,11t,13t}$, $sn-3-C_{18:3\;9c,11t,13t}$ and $sn-1-C_{18:0}$, $sn-2-C_{18:3\;9c,11t,13t}$, $sn-3-C_{18:3\;9c,11t,13t}$, respectively, and minor TG species of $(C_{18:2{\omega}6})(C_{18:3\;9c,11t,13c})_{2}$ and $(C_{18:1{\omega}9})(C_{18:2{\omega}6})(C_{18:3\;9c,11t,13c})$ contained mostly $sn-1-C_{18:2{\omega6}$, $sn-2-C_{18:3\;9c,11t,13t}$, $sn-3-C_{18:3\;9c,11t,13t}$ and $sn-1-C_{18:1{\omega}9}$, $sn-2-C_{18:2{\omega}6}$, $sn-3-C_{18:3\;9c,11t,13t}$. The TG fraction of the seed oils of Aleurites fordii was mostly occupied with simple TG species of $(C_{18:3\;9c,11t,13t})_{3}$, along with minor species of $(C_{18:2{\omega}6})(C_{18:3\;9c,11t,13t})_{2}$, $(C_{18:1{\omega}9})(C_{18:3\;9c,11t,13t})_{2}$ and $(C_{16:0})(C_{18:3\;9c,11t,13t})$. The sterospecific species of $sn-1-C_{18:2{\omega}6}$, $sn-2-C_{18:3\;9c,11t,13t}$, sn-3-C_{18:3\;9c,11t,13t}$, $sn-1-C_{18:1{\omega}9}$, $sn-2-C_{18:3\;9c,11t,13t}$, $sn-3-C_{18:3\;9c,11t,13t}$ and $sn-1-C_{16;0}$, $sn-2-C_{18:3\;9c,11t,13t}$, $sn-3-C_{18:3\;9c,11t,13t}$ are the main stereoisomers for the species of $(C_{18:2{\omega}6})(C_{18:3\;9c,11t,13t})_2$, $(C_{18:1{\omega}9})(C_{18:3\;9c,11t,13t})_{2}$ and $(C_{16:0})(C_{18:3\;9c,11t,13t})$, respectively.