• Title/Summary/Keyword: heterometallic salen

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Synthesis of Chiral Intermediates Catalyzed by New Chiral Polymeric (Salen) Cobalt Complexes Bearing Lewis Acidic Metal Halides

  • Lee, Kwang-Yeon;Kawthekar, Rahul B.;Kim, Geon-Joong
    • 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.

Enantioselective Phenolic Kinetic Resolution of Epoxides Catalyzed by New Chiral Salen Complexes (새로운 구조의 키랄 살렌 촉매상에서 페놀유도체에 의한 에폭사이드의 광학선택적 개환반응)

  • Rahul, B. Kawthekar;Lee, Kwang-Yeon;Kim, Geon-Joong
    • Applied Chemistry for Engineering
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    • v.18 no.6
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    • pp.630-635
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    • 2007
  • New chiral Co-salen complexes with one $C_3-^tBu$ group in the structure have been synthesized and applied as a chiral catalyst. A dimeric chiral salen having aluminum group metal salts such as $AlCl_3$ displayed very high catalytic reactivity and enantioselectivity for the asymmetric ring opening of epoxides to synthesize optically pure ${\alpha}$-aryloxy alcohols via phenolic kinetic resolution. The salen complexes immobilized on the inorganic support were also used as effective catalysts in that reaction. The identity of metal salts in the new chiral salen complex has proved to be important in the enantioselective reactions.

Cyanide- and Phenoxo-Bridged Heterobimetallic Fe(III)-Mn(III) Coordination Polymer: Synthesis, Crystal Structures and Magnetic Properties

  • Zhang, Daopeng;Kong, Lingqian;Li, Yueyun;Wang, Ping;Chen, Xia
    • Bulletin of the Korean Chemical Society
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    • v.35 no.9
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    • pp.2684-2688
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    • 2014
  • Two two-dimensional cyanide- and phenoxo-bridged heterometallic M(II)-Mn(III) (M = Ni, Pd) coordination polymers $\{[Mn(saltmen)]_4[Ni(CN)_4]\}(ClO_4)_2{\cdot}CH_3OH{\cdot}H_2O$ (1) and $\{[Mn(saltmen)]_4[Pd(CN)_4]\}(ClO_4)_2{\cdot}CH_3CN{\cdot}H_2O$ (2) ($saltmen^{2-}$ = N,N'-(1,1,2,2-tetramethylethylene)bis(salicylideneaminato)dianion) have been obtained by using $K_2[M(CN)_4]$ as building blocks and a salen-tpye Schiff-base manganese(III) compound as assembling segment. Single X-ray analysis reveals their isostrutural cyanide-bridged $MMn_4$ pentanuclear cationic structure. The four Schiff base manganese units of the pentanuclear entity are self-complementary through the phenoxo oxygen atoms from the neighboring complex, therefore forming cyanide- and phenoxo-bridged 2D sheet-like structure. Investigation over magnetic susceptibilities reveals the overall ferromagnetic coupling between the adjacent Mn(III) ions bridged by the phenoxo oxygen atoms with J = 2.13 and $2.21cm^{-1}$ for complexes 1 and 2, respectively.

Synthesis of Highly Enantiomerically Enriched Arenesulfonic Acid 2-Hydroxy Esters via Kinetic Resolution of Terminal Epoxides (속도론적 분할법을 통한 말단 에폭사이드로부터 고광학순도의 아렌술폰산 2-하이드록시 에스터의 합성)

  • Lee, Yae Won;Yang, Hee Chun;Kim, Geon-Joong
    • Applied Chemistry for Engineering
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    • v.27 no.5
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    • pp.490-494
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    • 2016
  • This paper describes the very efficient and highly enantioselective ring opening of terminal epoxides with alkyl and arene sulfonic acid. The dinuclear chiral (salen) Co complexes bearing Lewis acids of Al, Ga and In catalyze the reaction enantioselectively in the presence of tetrabutylammonium chloride using tert-butyl methyl ether as a solvent. The variation of the anion of the tetra butyl ammonium salt has significant impact on the reactivity and selectivity of the asymmetric ring opening of phenyl glycidyl ether with p-toluenesulfonic acid. The order of reactivity and selectivity was found to be $Cl^-$ > $l^-$ > $Br^-$ > $OH^-$. Strong synergistic effects of the different Lewis acid centers of Co-Al, Co-Ga and Co-In complexes were observed in the catalytic process. The dinuclear chiral salen catalyst containing $AlCl_3$ was found to be most active and highly enantioselective (91% ee).