• Bulletin of the Korean Chemical Society
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• v.31 no.4
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• pp.829-834
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• 2010

Ligand variation was carried out on a cobalt(III) complex of Salen-type ligand comprised of 1,2-cyclohexenediamine and salicylaldehyde bearing a methyl substituent on 3-position and -[$CMe(CH_2CH_2CH_2N^+Bu_3)_2$] on 5-position, which is a highly active catalyst for $CO_2$/propylene oxide copolymerization. Replacement of the methyl substituent with bulky isopropyl group resulted in alteration of the binding mode, consequently lowering turnover frequency significantly. Replacement with an ethyl group preserved binding mode and activity. Replacement of the tributylammonium unit with trihexylammonium or trioctylammonium, or replacement of 1,2-cyclohexenediamino unit with -$NC(Me)_2CH_2N$- decreased activity, even though the binding mode was unaltered.

• Bulletin of the Korean Chemical Society
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• v.28 no.9
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• pp.1553-1561
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• 2007

The new type of heterometallic chiral polymer salen complexes have been synthesized and it has been found that group 13 metal salts (AlCl3, GaCl3 and InCl3) combined to cobalt salen unit played the crucial role in the asymmetric kinetic resolution of racemic epoxides. Polymeric salen catalysts showed very high reactivity and enantioselectivity for the asymmetric ring opening of terminal epoxide with diverse nucleophiles. They provide the enantiopure useful chiral intermediates such as chiral terminal epoxides and α -aryloxy alcohols in one-step process. An efficient methodology for providing very high enantioselectivity can be achieved in the synthesis of valuable chiral building blocks via our catalytic system by combination of various asymmetric ring opening reactions.

• Korean Chemical Engineering Research
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• v.46 no.4
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• pp.769-776
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• 2008

The stereoselective synthesis of chiral terminal epoxide is of immense interest due to their utility as versatile starting materials as well as chiral intermediates. In this study, new chiral Co(salen) complexes bearing cobalt(II) chloride, iron(III) chloride and zinc(II) nitrate have been synthesized and characterized. The mass and EXAFS spectra provided the direct evidence of formation of complex. Their catalytic activity and selectivity have been demonstrated for the asymmetric ring opening of terminal epoxides such as styrene oxide and phenylglycidylether by hydrolytic kinetic resolution technology and for the synthesis of glycidyl buthylate. The easily prepared complexes exhibited very high enantioselectivity for the asymmetric ring opening of epoxides with $H_2O$ nucleophile, providing enantiomerically enriched terminal epoxides (>99% ee). The newly synthesized chiral salen showed remakablely enhanced reactivity with substantially low loadings. The system described in this work is very efficient for the sinthesis of chiral epoxide and 1,2-diol intermediates.

• Bulletin of the Korean Chemical Society
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• v.30 no.3
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• pp.745-748
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• 2009

• Korean Chemical Engineering Research
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• v.43 no.6
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• pp.647-661
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• 2005

The stereoselective synthesis of chiral terminal epoxide is of immense academic and industrial interest due to their utility as versatile starting materials as well as chiral intermediates. In this review, we investigate the research and development trend in the asymmetric ring opening reactions using cobalt salen catalysts. Hydrolytic kinetic resolution (HKR) technology is the very prominent way to prepare optically pure terminal epoxides among available methods. We have synthesized homogeneous and heterogeneous chiral dinuclear salen complexes and demonstrated their catalytic activity and selectivity for the asymmetric ring opening of terminal epoxides with variety of nucleophiles and for asymmetric cyclization to prepare optically pure terminal epoxides in one step. The resolved ring opened product combined with ring closing in the presence of base and catalyst afforded the enantioriched terminal epoxides in quantitaive yield. Potentially, these catalysts are using on an industrial scale to produce chiral intermediates. The experimental results of HKR technology applied to the synthesis of various chiral compounds are presented in this paper.

• Applied Chemistry for Engineering
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• v.30 no.3
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• pp.365-370
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• 2019

In this study, effects of the ultrasonic irradiation during the reaction process were investigated for the enantioselective kinetic resolution (EKR) reaction of racemic epoxides in the presence of chiral cobalt salen catalysts, as compared to that of using the conventional mechanical stirring. In order to compare catalytic activities, the chiral cobalt salen complexes having $AlCl_3-$, $BF_3-$ and nitrobenzenesulfonic acid (NBSA) were synthesized and used as catalysts, and then three kinds of the racemic epoxides such as ephichlorohydrine (ECH), epoxy phenoxypropane (EPP) and propylene oxide (PO) were used as reactants. In addition, EKR reactions have been performed using the water and methanol as nucleophiles, respectively. The unique contribution of ultrasonic irradiation as a powerful mixing medium was evaluated in this study to improve the kinetics in comparison to the conventional mechanical agitation during EKR reactions. The reaction time to obtain the highest 99 ee% became shorten more than that of above 60%, when the ultrasonic irradiation was used. This result may be interpreted by the cavitation effect of ultrasound in the solution, generating a powerful shear force for the very violent mixing.