• Title/Summary/Keyword: Cyclopropanation

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1,2-Ferrocenedilazaphosphinines 3:A New Class fo Planar Chiral Ligands for Cu-Catalyzed Cyclopropanation

  • Paek, Seung-Hwan;Co, Thanh Thien;Lee, Dong-Ho;Park, Yu-Chul;Kim, Tae-Jeong
    • Bulletin of the Korean Chemical Society
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    • v.23 no.12
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    • pp.1702-1708
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    • 2002
  • The synthesis and catalytic application of a new class of a new class of planar chiral ferrocenes, 1,2-ferrocenediylazaphosphinines (1 and 2) are described. They are powerful ligands for the copper(I)-catalyzed asymmetric cyclopropanation of a range of alkenes with diazo esters to exhibit an exceptionally high degree of diastereoselectivity(~100% de) in favor of trans isomers, regardless the structure of the olefins and the diazo compounds. Comparative studies between 1 and 2 reveal that the former works better in terms of diastereocontrol. In contrast, however, enantioselectivity is low with both 1 and 2 as a whole although, in certain cases with a proper combination of the olefin and the diazo ester, high optical yields (up to 100% ee) can be achieved. Other reaction parameters such as the reaction temperature and the structure of the ligand do exhibit some influence, although infinitestimal, on both chemical and optical yields.

Development of Ferrocene-Containing Metal Catalysts for Asymmetric Synthesis (페로센을 이용한 비대칭 유기합성용 금속 촉매의 개발)

  • Oh, Yunghee;Choi, Mi-Jin
    • Applied Chemistry for Engineering
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    • v.10 no.5
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    • pp.804-807
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    • 1999
  • New copper complexes with a ligand, L(L=N,N'-cyclohexane bis(ferrocenylmethylene)amine) which was obtained from ferrocene carboxaldehyde and 1,2-diaminocyclohexane with a mole ratio of 2:1, were prepared and characterized. Those were adapted to asymmetric catalysis. The copper(II) complexes do not work in cyclopropanation of styrene and ethyl diazoacetate but copper(I) complex catalyzes. The Cu(I)LOTf (OTf=trifluorometanesulfonate) shows a good regioselectivity giving high trans to cis ratio of up to 80:20.

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Chiral C2-Symmetric α-and ω-Diimines with Bulky Substituents at Nitrogen: Synthesis and Catalytic Properties of Some Copper Complexes

  • Park, Dong-Kyu;Ryu, Eun-Sook;Paek, Seung-Hwan;Shim, Sang-Chul;Cho, Chan-Sik;Kim, Tae-Jeong
    • Bulletin of the Korean Chemical Society
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    • v.23 no.5
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    • pp.721-726
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    • 2002
  • Two new C2-symmetric chiral $\alpha-$ and w-Diimines incorporating bulky ferrocenylethylamine and their copper(I)complexes have been synthesized and characterized by analytical and various spectroscopic techniques. The catalytic activities of these complexes have been tested in the asymmetric cyclopropanation of a series of olefins with some diazoacetates to achieve varying degree of dia- and enantio-selectivities depending on the nature of the ligand, the substrates, and the reagents. Some mechanistic implication has been made with regard to the interactions among all these chemical species.

A Study on the Synthesis and Property of Norbornane Type Carbocyclic Compounds that Include 3-membered Fused Ring System (삼각고리를 포함한 Norbornane 골격을 가진 화합물의 합성 및 물성에 관한 연구)

  • Oh Chang-Ho;Han Jeong-Sik;Park Dai-In;Ryu Joong-Hyun;Cho Joon-Hyun
    • Proceedings of the Korean Society of Propulsion Engineers Conference
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    • 2006.05a
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    • pp.202-205
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    • 2006
  • Some advanced nations have already developed and utilized high performance carbocyclic compounds as liquid fuel components. The common point of these compounds includes polycycles. We synthesized some promising compounds which include multiplex ring form. According to three kinds of cyclopropanation method, we could synthesize five target materials and measure their physical properties.

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Synthesis and Antiviral Activity of Novel C-Methyl Branched Cyclopropyl Nucleosides

  • Kwak, Eun-Yee;Hong, Joon-Hee;Park, Young-Jak;Choi, Bo-Gil
    • Archives of Pharmacal Research
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    • v.26 no.9
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    • pp.679-685
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    • 2003
  • A series of novel cyclopropyl nucleosides was synthesized using the highly stereoselective Simmons-Smith reaction starting from 1,2:5,6-di-Ο-isopropylidene-D-mannitol. The structural assignments of these nucleosides were determined by NMR studies and X-ray crystallography. All the synthesized nucleosides were assayed against several viruses.

Transition Metal-Catalyzed and -Promoted Reactions via Carbene and Vinylidene Complexes Generated from Alkynes

  • Ohe, Kouichi
    • Bulletin of the Korean Chemical Society
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    • v.28 no.12
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    • pp.2153-2161
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    • 2007
  • The transition metal-induced in situ generation of carbene complexes from alkynes having a carbonyl or imino group as a nucleophilic functionality has been investigated. These reactive carbenoid species are generated with high atom efficiency through a 6-endo-dig cyclization mode based on the electrocyclization of vinylidene complexes or a 5-exo-dig cyclization mode in π-alkyne complexes, and have been found to serve as versatile intermediates in catalytic carbene transfer reactions. Highlighted and reviewed in this account are the generation and preparation of pyranylidene, furylcarbene, pyrrolylcarbene, and vinylcarbene complexes and their application to [3,3]sigmatropic rearrangement of acylcyclopropylvinylidenes, catalytic cyclopropanation reactions, [2,3]sigmatropic rearrangement or condensation reactions via ylides, ring-opening and substitution reactions with heteroaromatic compounds, and catalytic isomerization of oligoynes.

Stereoselective Palladium Catalyzed Cyclizations of Enediyne Compounds

  • 오창호;임철윤;정형훈;정승현
    • Bulletin of the Korean Chemical Society
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    • v.20 no.6
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    • pp.643-647
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    • 1999
  • Hydropalladium carboxylates, formed from π-allylpalladium chloride dimer plus carboxylic acids, have been shown to catalyze cyclization of structurally diverse enediynes to form the corresponding six- or five-membered rings depending upon the reaction conditions. Some enediynes having an Oxygen linker in an appropriate position under the similar condition yielded the corresponding cyclopropanation products in highly stereoselective manner. A study using deuterated formic acid has proven that the alkylpalladium intermediates formed in our conditions were reduced by the pendant formate ligand. The dienediyne 10 yielded only the tricyclic product 12 in 67% yield, although it was expected to frrm the cyclic product 11. All these cyclizations seemed to occur via the corresponding alkylpalladium intermediates I. which could proceed to the corresponding cyclic products depending on the reaction conditions and the substrates. The study using ceuterated formic acid could provide an important information to understand the present cyclization mechanism. Overall the present study could play an important role in developing new synthetic methodologies for constructing complex polycyclic compounds.

Study on Properties of High Energetic and High Dense Cyclic Hydrocarbons by the Structure (고에너지 고밀도 고리탄화수소 화합물의 구조에 따른 물성 연구)

  • Cho, Joon-Hyun;Kwon, Tae-Soo;Jeong, Deok-Jin;Oh, Chang-Ho;Park, Dae-In;Han, Jeong-Sik
    • Proceedings of the Korean Society of Propulsion Engineers Conference
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    • 2008.11a
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    • pp.463-466
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    • 2008
  • The weapon systems with a liquid propulsion engine have been used for various purposes and demands of the liquid fuel with variety of properties for its operational purposes and environment. The cyclic hydrocarbons including norbornane or dicyclopentane structures have many applications to the guided weapon systems due to the high density and high energy characteristics, also efforts have been given in many fields. In this study, the cyclic hydrocarbons that we designed and fabricated were investigated to obtain tendency on the structures.

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