• Title/Summary/Keyword: Asymmetric synthesis

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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.

Synthesis of New Bimetallic Chiral Salen Catalyst Bearing Co(BF4)2 Salt and Its Application in Asymmetric Ring Opening of Epoxide

  • Kim, Yong-Suk;Lee, Choong-Young;Kim, Geon-Joong
    • Bulletin of the Korean Chemical Society
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    • v.31 no.10
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    • pp.2973-2979
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    • 2010
  • The newly synthesized homogeneous chiral Co(III) salen complexes were anchored non-covalently on the acidic sites of mesoporous Al-SBA-15. The Bronsted and Lewis acidic sites are attributed to the immobilization of fluorine functionalized chiral salen complexes on the supports. XRD, BET, TEM, FT-IR and ESCA (XPS) analyses were performed to characterize the property of support, and the structure of new homogeneous and heterogeneous chiral Co salen catalyst. The homogeneous and heterogeneous catalysts could be applied in asymmetric ring opening of epichlorohydrine (ECH) by water. They showed very high enantioselectivity and a good yield up to 99% in the catalytic synthesis of optically active products.

Synthesis of Asymmetric Dimer of Quinolone Derivatives Using p-TSA (p-TSA를 이용한 퀴놀론 유도체의 비대칭 이합체 합성)

  • 박명숙
    • YAKHAK HOEJI
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    • v.48 no.3
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    • pp.202-206
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    • 2004
  • New asymmetric dimers, N,N'-dialkyl-4'-hydroxy-4-oxo-2,2',3,3'-tetrahydro-2,2'-diphenyl-4,4'-quinolones 3a-f were synthesized through the dehydration and dea1coholation of N-alkylanilines and ethyl benzoylacetate. Dimers 3a-f were identified by NMR, IR and GC-MS. A series of dimer 3a-f has been synthesized using acid-catalyzed one-pot reaction that involved the condensation, cyc1ization and dimerization. Similarly, the 6,6'-methoxy (or 7,7'-methoxy) substituted dimers were prepared from N-alkyl-meta-(or para)-anisidines. Formation of dimers was undertaken with p-toluenesulfonic acid (p-TSA) at 90∼11$0^{\circ}C$ in toluene for 2∼6 hours over the Dean-Stark apparatus.

Synthesis of Pyrimidine Nucleosides as a Potential Asymmetric Catalysts (핵산유도체의 비대칭촉매 가능성연구)

  • Youn, In-Kwon;Beak, Gi-Hueon
    • The Journal of Natural Sciences
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    • v.9 no.1
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    • pp.95-104
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    • 1997
  • We synthesized the following series of 3', 5'hydroxy modified thymidine analogs to check the potential asymmetric catalytic effects. 3'-monomethylammino and dimethylaminothymidine was synthesized from thymidine via 8 step and 7 step in 38%, 20% overall yields respectively. 5'Acetyl-3'-dimethylamino thymidine was prepared from thymidine via 8 step in 40% overall yield. 5‘-TBS-3'-up-t BOC methylamino thymidine was prepared from thymidine via 6 step in 30% overall yield. 3'-acetyl-5'-t BOC amino thymidine was prepared from thymidine via 7 step in 31% overall yield.

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A Stereoselective Asymmetric Synthesis of Antibiotic (-)-Fumagillol Using Claisen Rearrangement and Intramolecular Ester Enolate Alkylation as Key Steps

  • Kim Deukjoon;Ahn Soon Kil;Bae Hoon;Kim Hak Sung
    • Archives of Pharmacal Research
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    • v.28 no.2
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    • pp.129-141
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    • 2005
  • (-)-Fumagillol (1), a hydrolysis product of fumagillin, has been synthesized by several group from commercially available 1,2:5,6-di-O-isopropylidene-${\alpha}$-D-allofuranose in a highly stereoselective manner. Chiral centers on C5 and C6 came from D-allofuranose and the asymmetric center on C4 was accomplished by 1,3-chirality transfer using the Claisen rearrangement on a chiral allyl alcohol. Chirality, which is necessary on an epoxide consisting of the spiro-ring system, was diastereoselectively constructed by the well-known reaction, intramolecular ester enolate alkylation (IEEA), which showed that this reaction can be applied to the alpha-alkoxy ester system. The epoxide on the side chain was regioselectively introduced by the difference between the number of substituents on the vinyl groups. This accomplishment proved that IEEA can be a useful tool for the synthesis of complex molecules.