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ACTIVATION OF METALS AND THEIR UTILIZATION FOR ORGANIC SYNTHESIS

ACTIVATION OF METALS AND THEIR UTILIZATION FOR ORGANIC SYNTHESIS
金属的活化及其在有机合成中的应用
批准号:
09450342
负责人:
TAKAI Kazuhiko
金额:
$8.77万
依托单位:
依托单位国家:
日本
项目类别:
Grant-in-Aid for Scientific Research (B)
财政年份:
1997
资助国家:
日本
项目状态:
已结题
起止时间:
1997 至 1999

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中文摘要
翻译
随后的立体声有机转化是用活性的锰物质或铬开发的(II)。(1)1-iodoalkyl triethlsilyl ether的治疗,衍生自an alkanal and Ety D23 yie D2SiI in dichlorometane, with a mixture of manganese and PbCI yie D22 yie D2 in THF generates a nonstabilized carbonyl ylide。通过[3+2]环肾上腺素反应与不饱和的化合物、如α、β-不饱和的esters、allylic ethers和aldehyde给予四氢呋喃衍生物(或二氧烷)。(2)微相对性铬(II)氯化物可以在烷基碘化、烷基基在铬(II)的存在中,烷基基本体的寿命如此长,以至于它可能是一种潜在的互分子添加到1,3-diene。快速的一个电子减少了在一种合金铬物种中形成的合金自由基结果,其中添加了一种替代品,从而产生了三个分量耦合产品。(3)α-chloroalkylboronic esters与CrCI-D22-D2在LiI和TMEDA产生α-boryl radicals中的治疗,其中添加到α, β-不饱和的esters在优秀年份中的1,4-时尚条件下。(4) A chromium hydride equivalent generated from CrCI-D22-D2, B-D212-D2, and water reacts regioselectively with 1,3-dienes to give allylic chromium reagents, and the reagents add to carbonyl compounds in a chemo-and stereoselective maner。(5)在醛到(E)-1-碘醇的立体声转化中的铬盐的催化循环,用锌、Mey D23 y D2 SiCI和Dioxane中的NaI组装。(6) Iodoform is reduced with manganese in the presence of Me的D23的D2 SiCI to give Me的D23的D2 SiCHI的D22的D2。一个从一罐到(E)-1-烯基三甲基硅烷转化为一罐,然后以碘形式、芒果、Me-D23-SiCI和一个催化量的铬(II)THF中的氯化物通过我的原位形成-D23-D2 SiCHI-D22-D2-D2-D2-D2。
英文摘要
The following stereoselective organic transformations have developed with an activated manganese matal or chromium (II). (1) Treatment of 1-iodoalkyl triethlsilyl ether, derived from an alkanal and EtィイD23ィエD2SiI in dichloromethane, with a mixture of manganese and PbCIィイD22ィエD2 in THF generates a nonstabilized carbonyl ylide. The ylide reacts with unsaturated compounds, such as α, β-unsaturated esters, allylic ethers, and an aldehyde, to give tetrahydrofuran derivatives (or a dioxolane) via [3+2] cycloadditon reactions. (2) The mild reluctant chromium (II) chloride can discriminate between alkyl iodides, alkyl radicals, and allylic radicals. In the presence of chromium (II) the alkyl radical is so long-lived that it can undergo intermolecular addition to a 1, 3-diene. Rapid one-electron reduction of the formed allylic radical results in an allylic chromium species, which adds to an aldehyde to afford a three-component coupling product. (3) Treatment of α-chloroalkylboronic esters with CrCIィイD22ィエD2 in the presence of LiI and TMEDA generates α-boryl radicals, which add to α, β-unsaturated esters in a 1, 4-fashion under mild conditions in excellent yields. (4) A chromium hydride equivalent generated from CrCIィイD22ィエD2, BィイD212ィエD2, and water reacts regioselectively with 1, 3-dienes to give allylic chromium reagents, and the reagents add to carbonyl compounds in a chemo- and stereoselective manner. (5) A catalytic cycle of a chromium salt in a stereoselective transformation of aldehydes to (E)-1-iodoalknens using a geminal dichromium reagent, is assembled with zinc, MeィイD23ィエD2SiCI, and NaI in dioxane. (6) Iodoform is reduced with manganese in the presence of MeィイD23ィエD2SiCI to give MeィイD23ィエD2SiCHIィイD22ィエD2. A one-pot transformation of aldehydes to (E)-1-alkenyltrimethylsilanes is then performed with iodoform, manganese, MeィイD23ィエD2SiCI, and a catalytic amount of chromium(II) chloride in THF via in situ formation of MeィイD23ィエD2SiCHIィイD22ィエD2.
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会议论文
K. Takai,: "Improved Synthesis and Crystal Structure of TiCl3(tmeda)(thf) : A Highly Stereoselective Pinacol Coupling Reagent for Aromatic Aldehydes"Chem. Lett.. (印刷中). (2000)
K. Takai,:“TiCl3(tmeda)(thf) 的改进合成和晶体结构:芳香醛的高度立体选择性频哪醇偶联试剂”Chem. (2000 年出版)。
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通讯作者:
K. Takai, N. Shinoyama, M. Ohta: "Generation of α-Boryl Radicals by Reduction of α-Haloalkylboronic Esters with CrCl_2"Synlett. 253-254 (1998)
K. Takai、N. Shinoyama、M. Ohta:“用 CrCl_2 还原 α-卤代烷基硼酯生成 α-硼基自由基”Synlett 253-254 (1998)。
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通讯作者:
K.Takai,T.Ichiguchi,S.Hikasa: "A Practical Transformation of Aldehydes into (E)-Iodoalkenes with Geminal Dichromium Reagents"Synlett. 8号. 1268-1270 (1999)
K. Takai、T. Ichiguchi、S. Hikasa:“使用孪生二铬试剂将醛实际转化为 (E)-碘代烯烃”Synlett,第 8 期。1268-1270 (1999)
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通讯作者:
K. Takai, C. Toratsu: "B_<12>-Catalyzed Generation of Allylic Chromium Reagents from 1,3-Dienes, CrCl_2 and Water"J. Org. Chem.. 63. 6450-6451 (1998)
K. Takai,C. Toratsu:“B_12-催化从 1,3-二烯、CrCl_2 和水生成烯丙基铬试剂”J。
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共 26 条
    Development of New Catalytic Activities of Rhenium Complexes and Their Applications
    • 批准号:
      19350049
    • 项目类别:
      Grant-in-Aid for Scientific Research (B)
    • 资助金额:
      $12.4万
    • 财政年份:
      2007
    • 负责人:
      TAKAI Kazuhiko
    • 依托单位:
    Efficient Organic Reactions by Dynamic Control of Early Transition Metal Complexes
    • 批准号:
      14078219
    • 项目类别:
      Grant-in-Aid for Scientific Research on Priority Areas
    • 资助金额:
      $18.18万
    • 财政年份:
      2002
    • 负责人:
      TAKAI Kazuhiko
    • 依托单位:
    Development of Novel Stereoselective Pinacol Coupling Reactions
    • 批准号:
      12450365
    • 项目类别:
      Grant-in-Aid for Scientific Research (B)
    • 资助金额:
      $9.6万
    • 财政年份:
      2000
    • 负责人:
      TAKAI Kazuhiko
    • 依托单位:
    SEQUENTIAL GENERATION OF CARBON RADICALS AND CARBANIONS : DYNAMIC STEREOCONTROL IN THE REACTION SEQUENCE
    • 批准号:
      10208212
    • 项目类别:
      Grant-in-Aid for Scientific Research on Priority Areas (B)
    • 资助金额:
      $13.89万
    • 财政年份:
      1998
    • 负责人:
      TAKAI Kazuhiko
    • 依托单位:
    海外基金