• Journal of Microbiology and Biotechnology
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• 제25권10호
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• pp.1634-1639
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• 2015

Cytochrome P450 hydroxylase (CYP) in actinomycetes plays an important role in the biosynthesis and bioconversion of various secondary metabolites. Two unique CYPs named CYP-sb21 and CYP-pa1, which were identified from Sebekia benihana and Pseudonocardia autotrophica, respectively, were proven to transfer a hydroxyl group at the 4^th or 9^th N-methyl leucine position of immunosuppressive agent cyclosporin A (CsA). Interestingly, these two homologous CYPs showed different CsA regio-selectivities. CYP-sb21 exhibited preferential hydroxylation activity at the 4^th position over the 9^th position, whereas CYP-pa1 showed the opposite preference. To narrow down the CYP domain critical for CsA regio-selectivity, each CYP was divided into four domains, and each domain was swapped with its counterpart from the other CYP. A total of 18 hybrid CYPs were then individually tested for CsA regio-selectivity. Although most of the hybrid CYPs failed to exhibit a significant change in regio-selectivity in the context of CsA hydroxylation, hybrid CYP-pa1 swapped with the second domain of CYP-sb21 showed a higher preference for the 9^th position. Moreover, hybrid CYPsb21 containing seven amino acids from the 2nd domain of CYP-pa1 showed higher preference for the 4^th position. These results imply that the 2nd domain of CsA-specific CYP plays a critical role in CsA regio-selectivity, thereby setting the stage for biotechnological application of CsA regio-selective hydroxylation.

• Bulletin of the Korean Chemical Society
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• 제31권7호
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• pp.1837-1838
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• 2010

• Bulletin of the Korean Chemical Society
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• 제25권10호
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• pp.1463-1464
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• 2004

• Bulletin of the Korean Chemical Society
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• 제28권12호
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• pp.2139-2152
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• 2007

Ruthenium complex-catalyzed reactions often require highly qualified tuning of reaction conditions with substrates to attain high yield and selectivity of the products. In this review, our strategies for achieving characteristic ruthenium complex-catalyzed co-oligomerization of different alkenes are disclosed: 1) The codimerization of 2-norbornenes with acrylic compounds by new ruthenium catalyst systems of RuCl3(tpy)/Zn [tpy = 2,2':6',2''-terpyridine] or [RuCl2(η6-C6H6)]2/Zn in alcohols, 2) A novel synthesis of 2-alkylidenetetrahydrofurans from dihydrofurans and acrylates by zerovalent ruthenium catalysts, such as Ru(η4-cod)(η6-cot) [cod = 1,5-cyclooctadiene, cot = 1,3,5-cyclooctatriene] and Ru(η6-cot)(η2-dmfm)2 [dmfm = dimethyl fumarate], 3) Regio- and stereoselective synthesis of enamides by Ru(η6-cot)(η2-dmfm)2-catalyzed codimerization of N-vinylamides with alkenes, and 4) Unusual head-to-head dimerization of styrenes and linear codimerization of styrenes with ethylene by Ru(η6-cot)(η2-dmfm)2 catalyst in the presence of primary alcohols.