Catalytic asymmetric synthesis of optically active amines and their derivatives

催化不对称合成光学活性胺及其衍生物

基本信息

  • 批准号:
    10640579
  • 负责人:
  • 金额:
    $ 2.11万
  • 依托单位:
  • 依托单位国家:
    日本
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
  • 财政年份:
    1998
  • 资助国家:
    日本
  • 起止时间:
    1998 至 1999
  • 项目状态:
    已结题

项目摘要

For the development of the asymmetric synthesis of optically active amines and their derivatives, we examined the enanioselective addition of trimethylsilyl cyanide to a variety of N-substituted imines. At first, we investigated the reaction catalyzed by chiral Schiff base-titanium alkoxide complexes which was very effective for enantioselective trimethylsilylcyanation of aldehydes. We found that by using chiral titanium complexes, high chemical yield was attained, but only unsatisfied optical yield (20% ee) was obtained. The chiral titanium complex bearing chiral binaphthol derivatives was also found to give only low optical yield. Then we examined the reaction catalyzed by cationic chiral BINAP- palladium complex. By using complex of in-situ preparation and isolated one, low optical yield was obtained in both cases though chemical yield was high. Based on the above results we changed the strategy for the synthesis of optically active amines, that is, catalytic asymmetric allylic amination catalyzed by palladium complexes. We have succeeded in the synthesis of novel palladium catalyst having P, N-bidentate ligands. These new catalyst was found to have high catalytic activity and enantioselectivity in catalytic allylic alkylation. The optical yields of the allylic alkylation products were over 80% ee. At present, the asymmetric amination is being examined.
为了发展光学活性胺及其衍生物的不对称合成,我们研究了三甲基硅腈对各种N-取代亚胺的不对称加成反应。首先,我们研究了手性席夫碱-钛醇盐配合物催化的醛的三甲基硅腈化反应。我们发现,使用手性钛配合物,获得了高的化学产率,但只有不满意的光学产率(20%ee)。手性钛配合物轴承手性联萘衍生物也被发现,只有低的光学产率。然后考察了阳离子手性BINAP-钯配合物催化的反应.采用原位合成的配合物和单独合成的配合物,虽然化学产率较高,但光学产率较低。基于上述结果,我们改变了光学活性胺的合成策略,即钯配合物催化的不对称烯丙基胺化反应。我们成功地合成了具有P,N-双齿配体的新型钯催化剂。这些催化剂在催化烯丙基烷基化反应中具有较高的催化活性和对映选择性。烯丙基烷基化产物的光学产率在80%ee以上。目前,不对称胺化反应正在研究中。

项目成果

期刊论文数量(28)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
M.Hayashi: "Metal Catalyzed Transfomation of D-Glucal to Optically Active Furan Diol"Chem.Commun.. 965-966 (1999)
M.Hayashi:“金属催化 D-葡萄糖醛转化为光学活性呋喃二醇”Chem.Commun.. 965-966 (1999)
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    0
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M. Hayashi, K. Yamada, and S. Nakayama: "Dehydrogenation Reactions by Palladium Supported on Activated Charcoal under Ethylene Atmosphere : Synthesis of 1, 5-Anhydrohex-1-en-3-uloses."Synthesis. 1869-1871 (1999)
M. Hayashi、K. Yamada 和 S. Nakayama:“乙烯气氛下活性炭负载钯的脱氢反应:1, 5-AnHydrohex-1-en-3-ulose 的合成”。 合成。
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    0
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M.Hayashi: "Efficient Synthesis of Carbohydrate-containing Carbocyclic Compounds Based on Palladium-catalyzed Vinylation of Sugars and Subsequent Diels-Alder Reaction"Tetrahedron. 55. 12287-12294 (1999)
M.Hayashi:“基于钯催化糖乙烯基化和随后的狄尔斯-阿尔德反应的含碳水化合物碳环化合​​物的高效合成”四面体。
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    0
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0.Loiseleur: "Enantioselective Heck Reactions using Chiral P,N-ligands in "Perspective in Organopalladium Chemistry for XXI Century""Elsevier. 7 (1999)
0.Loiseleur:“《二十一世纪有机钯化学展望》中使用手性 P,N-配体的对映选择性赫克反应”,Elsevier。
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  • 影响因子:
    0
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  • 通讯作者:
M.Hayashi: "Dehydrogenation Reactions by Palladium Supported on Activated Charcoal under Ethylene Atmosphere: Synthesis of 1,5-Anhydrohex-1-en-3-uloses"Synthesis. 1869-1871 (1999)
M.Hayashi:“乙烯气氛下活性炭负载钯的脱氢反应:1,5-AnHydrohex-1-en-3-ulose 的合成”。
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    0
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HAYASHI Masahiko其他文献

HAYASHI Masahiko的其他文献

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{{ truncateString('HAYASHI Masahiko', 18)}}的其他基金

Air-borne in-situ observation for vertical mixing process of aerosols over coastal region of Antarctic continent
南极大陆沿海地区气溶胶垂直混合过程机载原位观测
  • 批准号:
    24403001
  • 财政年份:
    2012
  • 资助金额:
    $ 2.11万
  • 项目类别:
    Grant-in-Aid for Scientific Research (B)
In-situ observation of stratospheric aerosol using balloon assisted gliding UAV
气球辅助滑翔无人机对平流层气溶胶的原位观测
  • 批准号:
    23651019
  • 财政年份:
    2011
  • 资助金额:
    $ 2.11万
  • 项目类别:
    Grant-in-Aid for Challenging Exploratory Research
The Analysis on popular pictures from the Middle Age to the modern era based on the text of literature in the same age
基于同时代文学文本的中古至现代流行图画分析
  • 批准号:
    21520207
  • 财政年份:
    2009
  • 资助金额:
    $ 2.11万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
High Dispersion Infrared Spectroscopy for Detecting Extrasolar Terrestrial Planets
用于探测太阳系外类地行星的高色散红外光谱
  • 批准号:
    21244022
  • 财政年份:
    2009
  • 资助金额:
    $ 2.11万
  • 项目类别:
    Grant-in-Aid for Scientific Research (A)
Microscopic studies of electronic quantum condensed state in nano-structures
纳米结构中电子量子凝聚态的微观研究
  • 批准号:
    18540335
  • 财政年份:
    2006
  • 资助金额:
    $ 2.11万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
New Approach for Complete Reversal of Enantioselectivity Using a Single Chiral Source
使用单一手性源完全逆转对映选择性的新方法
  • 批准号:
    17350020
  • 财政年份:
    2005
  • 资助金额:
    $ 2.11万
  • 项目类别:
    Grant-in-Aid for Scientific Research (B)
Accounting Systems and Performance Evaluation for Nonprofit Organizations
非营利组织的会计制度和绩效评估
  • 批准号:
    14597015
  • 财政年份:
    2002
  • 资助金额:
    $ 2.11万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
Observation of spatial distributions of aerosol characteristics by the satellite sensor and the airborne systems.
通过卫星传感器和机载系统观测气溶胶特征的空间分布。
  • 批准号:
    14048225
  • 财政年份:
    2002
  • 资助金额:
    $ 2.11万
  • 项目类别:
    Grant-in-Aid for Scientific Research on Priority Areas
Development of dehydrogenation reaction using palladium catalyst and ethylene system
钯催化剂与乙烯体系脱氢反应的进展
  • 批准号:
    13554022
  • 财政年份:
    2001
  • 资助金额:
    $ 2.11万
  • 项目类别:
    Grant-in-Aid for Scientific Research (B)
A Comparative Study of the Relationship between Literature and Pictures in China, Korea, and Japan
中、韩、日文学与图像关系比较研究
  • 批准号:
    09610446
  • 财政年份:
    1997
  • 资助金额:
    $ 2.11万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)

相似海外基金

SBIR Phase I: A chemical assay kit for the high-throughput screening of chiral amine enantiomeric excess
SBIR 第一阶段:用于高通量筛选手性胺对映体过量的化学检测试剂盒
  • 批准号:
    1843626
  • 财政年份:
    2019
  • 资助金额:
    $ 2.11万
  • 项目类别:
    Standard Grant
Development of the construction of multi contiguous chiral carbons by using recyclable chiral amine.
利用可回收手性胺开发多连续手性碳的构建。
  • 批准号:
    22590024
  • 财政年份:
    2010
  • 资助金额:
    $ 2.11万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
New Stereoselective Reactions for Chiral Amine Synthesis
手性胺合成的新立体选择性反应
  • 批准号:
    8110644
  • 财政年份:
    2009
  • 资助金额:
    $ 2.11万
  • 项目类别:
New Stereoselective Reactions for Chiral Amine Synthesis
手性胺合成的新立体选择性反应
  • 批准号:
    8267696
  • 财政年份:
    2009
  • 资助金额:
    $ 2.11万
  • 项目类别:
New Stereoselective Reactions for Chiral Amine Synthesis
手性胺合成的新立体选择性反应
  • 批准号:
    7817116
  • 财政年份:
    2009
  • 资助金额:
    $ 2.11万
  • 项目类别:
Development of highly selective synthetic methodology using axially chiral amine organocatalysts
使用轴向手性胺有机催化剂开发高选择性合成方法
  • 批准号:
    20750030
  • 财政年份:
    2008
  • 资助金额:
    $ 2.11万
  • 项目类别:
    Grant-in-Aid for Young Scientists (B)
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