• Journal of Microbiology and Biotechnology
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• 제18권5호
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• pp.901-907
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• 2008

Thermotoga neapolitana $\beta$-glucosidase (BglA) was subjected to site-directed mutagenesis in an effort to increase its ability to synthesize arbutin derivatives by transglycosylation. The transglycosylation reaction of the wild-type enzyme displays major ${\beta}(1,6)$ and minor ${\beta}(1,3)$ or ${\beta}(1,4)$ regioselectivity. The three mutants, N291T, F412S, and N291T/F412S, increased the ratio of transglycosylation/hydrolysis compared with the wild-type enzyme when pNPG and arbutin were used as a substrate and an acceptor, respectively. N291T and N219T/F412S had transglycosylation/hydrolysis ratios about 3- and 8-fold higher, respectively, than that of the wild-type enzyme. This is due to the decreased hydrolytic activity of the mutant rather than increased transglycosylation activity. Interestingly, N291T showed altered regioselectivity, as well as increased transglycosylation products. TLC analysis of the transglycosylation products indicated that N291T retained its ${\beta}(1,3)$ regioselectivity, but lost its ${\beta}(1,4)$ and ${\beta}(1,6)$ regioselectivity. The altered regioselectivity of N291T using two other acceptors, esculin and salicin, was also confirmed by TLC. The major transglycosylation products of the wild type and N291T mutant were clearly different. This result suggests that Asn-291 is highly involved in the catalytic mechanism by controlling the transglycosylation reaction.

• Archives of Pharmacal Research
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• 제14권4호
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• pp.364-369
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• 1991

The synthesis and regioselective reactions of a chiral allyl sulfide. (S)-(+)-(1-methylpyrrolidin-2-yl)methyl allyl sulfide (MAS, 1) are described. Remarkable ${\alpha}-regioselectivity$ was observed in the alkylation of the carbanion of MAS while 1:3 mixtures of ${\alpha}-and\;{\gamma}-adducts$ were produced in the addition of the MAS anion to aldehydes. However, a dramatic change of the regioselectivity was witnessed when Lewis acids such as $Et_3Al$, $Et_3B$, and $Ti(O^iPr)_4$ were used as additives in the addition reaction. In these cases, ${\alpha}-adducts$ were formed exclusively. A rationale for the change of regioselectivity is provided. And the stereochemical aspect of the addition reaction is also described.

• 대한화학회지
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• 제23권5호
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• pp.286-295
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• 1979

非對稱으로 置環된 diene과 dienophile 間의 反應에서 配向性에 미치는 산촉매의 효과를 豫期하기 위해서 루이스酸과 錯物을 形成한 dienophile의 理論的모델에 FMO 理論을 적용하여CNDO/2 방법으로 고찰하였다. 電子的性質이 類似한 치환기로 치환된 diene, dienophile의 반응(즉, 電子不足 diene과 電子不足 dienophile의 반응)에서 일어나는 半極性 고리化반응을 제외한 주어진 대부분의 반응에 대해서, CNDO/2방법이 실험적인 配向性과 一致하는 좋은 결과를 주었다. 또한 二次軌道相互作用이 非對稱으로 치환된 diene과 dienophile의 Diels-Alder 반응의 배향성에 중요한 역할을 했다는 사실을 보여주었다. Anh의 방법이 다른 방법보다 수식적으로 간단할지라도, 非對稱전이상태를 강조한 Anh의 방법이 配向性 결정에 좋은 결과를 주었다.

• Bulletin of the Korean Chemical Society
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• 제28권12호
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• pp.2248-2252
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• 2007

SOMT-9 is an O-methyltransferase that utilizes quercetin to produce 3'-methoxy quercetin. In order to determine which amino acids of SOMT-9 are important for this reaction and its regioselectivity, molecular docking experiments followed by site directed mutagenesis were performed. Molecular modeling and molecular docking experiments identified several amino acid residues involved in metal binding, AdoMet binding, and substrate binding. Site-directed mutagenesis showed that Asp188 is critical for metal binding and that Lys165 assists other metal binding residues in maintaining quercetin in the proper position during the reaction. In addition, Tyr207 was shown to play an important role in the determination of the regioselectivity and Met60 was shown to be involved in formation of the hydrophobic pocket necessary for substrate binding. The molecular modeling and docking experiments discussed in this study could be applicable to future research including prediction of substrate binding and regioselectivity of an enzyme.

• 공업화학
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• 제10권5호
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• pp.804-807
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• 1999

페로센 카르복시알데히드와 1,2-diaminocyclohexane을 2:1로 반응시켜 키랄 리간드 L(L=N,N'-cyclohexane bis(ferrocenylmethylene)amine)을 합성하고 이를 구리와 반응시켜 새로운 구리 착물을 합성하였다. 이 착물들을 확인하고 비대칭 유기 합성반응에 촉매로 사용하였다. 구리(II) 착물들은 스티렌과 에틸디아조아세테이트와의 시클로프로판화 반응에서 촉매작용을 하지 않았으나 구리(I)화합물, Cu(I)LOTf (OTf=trifluoromethanesulfonate)는 시클로프로판 생성물 trans:cis의 비율에 있어 80:20 이상의 높은 regioselectivity를 보였다.

• 대한화학회지
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• 제56권1호
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• pp.175-179
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• 2012

• Bulletin of the Korean Chemical Society
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• 제31권8호
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• pp.2143-2146
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• 2010

A selective synthetic method of the 2,5-biaryltriazolones has been developed via copper-catalyzed N-arylation reaction. Aryltriazolones, which were readily prepared from commercially available compounds, were N-arylated to 2,5-biaryltriazolones with high regioselectivity. This approach allows for access to a variety of 2,5-biaryl-1,2,4-trizol-3-ones in a simple and practical manner.

• Bulletin of the Korean Chemical Society
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• 제35권6호
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• pp.1851-1854
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• 2014

• Journal of Microbiology and Biotechnology
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• 제20권3호
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• pp.574-578
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• 2010

Archaebacteria Sulfolobus acidocaldarius contains the highly thermophilic cytochrome P450 enzyme (CYP119). CYP119 possesses stable enzymatic activity at up to $85^{\circ}C$. However, this enzyme is still considered as an orphan P450 without known physiological function with endogenous or xenobiotic substrates. We characterized the regioselectivity of lauric acid by CYP119 using the auxiliary redox partner proteins putidaredoxin (Pd) and putidaredoxin reductase (PdR). Purified CYP119 protein showed a tight binding affinity to lauric acid ($K_d=1.1{\pm}0.1{\mu}M$) and dominantly hydroxylated (${\omega}-1$) position of lauric acid. We determined the steady-state kinetic parameters; $k_{cat}$ was 10.8 $min^{-1}$ and $K_m$, was 12 ${\mu}M$. The increased ratio to $\omega$-hydroxylated production of lauric acid catalyzed by CYP119 was observed with increase in the reaction temperature. These studies suggested that the regioselectivity of CYP119 provide the critical clue for the physiological enzyme function in this thermophilic archaebacteria. In addition, regioselectivity control of CYP119 without altering its thermostability can lead to the development of novel CYP119-based catalysts through protein engineering.

• 대한화학회지
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• 제45권6호
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• pp.538-545
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• 2001

전자끌게 치환기를 함유하고 있는 몇 가지 대표적인 biphenyl 유도체의 니트로화 반응 생성물의 이성질체 비율을 조사하였다. 이성질체를 분리하여 각각의 $^1H$ NMR을 얻고 이를 근거로 반응 후 생성되는 혼합물의 $^1H$ NMR을 정량적으로 분석함으로서 이성질체의 생성비율을 결정하는 효율적인 방법을 확립하였다. 분리가 어려운 니트로 화합물의 경우 니트로를 아민으로 환원하고, 카르복실기는 에틸 에스테르로 전환하여 분리할 수 있었다. 이성질체의 생성비율을 향상시키기 위하여 몇 가지 대표적인 반응조건에서 니트로화 반응을 수행하였으며 확립된 방법을 이용하여 각 이성질체의 비율을 정확히 결정할 수 있었다. 반응 조건에 따라 또는 치환기의 위치 및 종류에 따라 위치 선택성이 상당히 다른 결과를 보였다.