ASYMMETRIC ALLYLATION REACTION OF IMINES WITH CHIRALLY MODIFIED ALLYLMETALS

亚胺与手性改性烯丙基金属的不对称烯丙基化反应

基本信息

  • 批准号:
    09650955
  • 负责人:
  • 金额:
    $ 1.98万
  • 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:
    1997
  • 资助国家:
    日本
  • 起止时间:
    1997 至 1998
  • 项目状态:
    已结题

项目摘要

Although the enantioselective synthesis of optically active amines by nucleophilic addition of organometallic reagents is a topic of current interest, the enantioselective addition of allylmetals to C=N double bond is quite underdeveloped in comparison to the effort on record in the area of asymmetric addition to carbonyl compounds. This research project aimed at design of asymmeric allylat ion reaction of imines, We have found that N-metallo imines such as N-silyl, N-aluminum, and N-borylimines were allylated with allylboron reagents to give the corresponding homoallylamines in good yield. Removal of N-substituents from the homoallylamines were quite easy. This approach is thus a novel efficient method for the synthesis of optically active primary homoallylamines. For example, N-silylimines were enantioselectively allylated with chirally modified allylboron reagent to give the homoallylamines in almost quantitative yield with high enantioselectivity (> 90% ee). To our knowledge, this … More is the first report of high level of asymmetric induction realized in the enantioselective addition of allylboron reagent to imines. Although N-silylimines derived from enolizable aldehydes resulted in the formation of complexed mixture as the product of allylat ion, N-alumino imines having alpha-proton could be allylated to give the homoallylamine. In the cases of the enantioselective allylation of N-alumino imines and N-boryl imines afforded the enantioenriched homoallylamines in good yield with high selectviity. It is noteworthy that high enantioselectivty (>80% ee) was attained even at room temperature when these imines were allylated.Polymer-supported chiral reagents and catalysts are of interest in the field of asymmetric synthesis, since the chiral reagents can be recycled many times. In some cases, continuous flow system is possible by using polymer-suppored chiral catalyst. We have prepared polymer- supported chirally modified allylboron reagents. Asymmetric allylation of N-metallo imines described above with the polymer-supported reagents have been investigated. Polymer- supported N-sulfonylaminoalcohols derived from D-camphor or norephedrine were quite suitable chiral ligands for the allylation of imines. In spite of heterogeneous reaction using such polymers, sufficient reactivity and high enantioselelctivity was attained. This is also the first finding of the enantioselective allylation of imines using polymeric reagent. Less
虽然通过有机金属试剂的亲核加成反应对映选择性合成光学活性胺是当前感兴趣的课题,但与羰基化合物的不对称加成相比,烯丙基金属对C=N双键的不对称加成反应还相当不发达。本研究旨在设计亚胺的不对称烯丙基化反应,我们发现N-金属亚胺如N-硅基亚胺、N-铝基亚胺和N-硼基亚胺与烯丙基硼试剂烯丙基化得到相应的高烯丙基胺,产率较高。从高烯丙基胺上除去N-取代基是相当容易的。该方法是一种合成光学活性高烯丙基伯胺的有效方法。例如,用手性修饰的烯丙基硼试剂对N-甲硅烷基亚胺进行对映选择性烯丙基化,以几乎定量的产率和高对映选择性(> 90%ee)得到高烯丙基胺。据我们所知,这 ...更多信息 首次报道了烯丙基硼试剂对亚胺的不对称加成反应。虽然由可烯醇化的醛衍生的N-甲硅烷基亚胺作为烯丙基化的产物导致形成络合混合物,但具有α-质子的N-铝亚胺可以烯丙基化以得到高烯丙基胺。在对映选择性烯丙基化反应中,N-铝亚胺和N-硼亚胺以高收率和高选择性得到了对映体富集的高烯丙基胺。这些亚胺在室温下进行烯丙基化反应,都具有较高的对映选择性(> 80%ee),手性试剂和催化剂可以多次循环使用,因此在不对称合成领域具有重要的应用价值。在某些情况下,通过使用聚合物负载的手性催化剂,连续流动系统是可能的。制备了聚合物支载的手性烯丙基硼试剂.已经研究了上述N-金属亚胺与聚合物负载的试剂的不对称烯丙基化。由D-樟脑或去甲麻黄碱衍生的高分子负载的N-磺酰氨基醇是非常适合的亚胺烯丙基化反应的手性配体。尽管使用这种聚合物的非均相反应,但获得了足够的反应性和高的对映选择性。这也是首次发现用高分子试剂进行亚胺的不对称烯丙基化反应。少

项目成果

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A.A.El-Shehawy, M.A.Omara, K.Ito and S.Itsuno: ""Preparation of Both Diastereomers of Homoallylic Amines by Allylation of Methyl N-Benzylidene- (S) -valinate"" Synlett. 367-368 (1998)
A.A.El-Shehawy、M.A.Omara、K.Ito 和 S.Itsuno:“通过 N-亚苄基-(S)-缬氨酸甲酯的烯丙基化制备同烯丙基胺的两种非对映异构体”Synlett。
  • DOI:
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  • 影响因子:
    0
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  • 通讯作者:
K.Watanabe: "Enantioselective synthesis of optically active homoallylamines by allylboration of N-diisobutylaluminum imines" Journal of Organometallic Chemistry. (in press). (1999)
K.Watanabe:“通过 N-二异丁基铝亚胺的烯丙基硼化对光学活性高烯丙胺进行对映选择性合成”《有机金属化学杂志》。
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    0
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A.A.El-Shehawy, M.Y.Abdelaal, K.Watanabe, K.Ito and S.Itsuno: ""Enantioselective Allylation of N- (Trimethylsilyl) benzaldehyde Imine using Polymer-Supported chiral Allyboron Regents"" Tetrahedron : Asymmetry. 8. 1731-1734 (1997)
A.A.El-Shehawy、M.Y.Abdelaal、K.Watanabe、K.Ito 和 S.Itsuno:“使用聚合物支持的手性 Allyboron 试剂对 N-(三甲基甲硅烷基)苯甲醛亚胺进行对映选择性烯丙基化”四面体:不对称性。
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    0
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K.Watanabe, S.Kuroda, A.Yokoi, K.Ito and S.Itsuno: ""Enantioselective Synthesis of Optically Active Homoallylamines by Allyboration of N-Diisobutylaluminum Imines"" J.Organomet.Chem.(in press).
K.Watanabe、S.Kuroda、A.Yokoi、K.Ito 和 S.Itsuno:“通过 N-二异丁基铝亚胺的烯丙基硼化对映选择性合成光学活性高烯丙胺””J.Organomet.Chem.(出版中)。
  • DOI:
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  • 影响因子:
    0
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  • 通讯作者:
S.Itsuno他: "Enantiopure N-Sulfonylamino Alcohols and Their Copolymers as Chiral Auxiliaries for the Highly Enantioselective Allylboration" Reactive & Functional Polymers. (1998)
S. Itsuno 等人:“对映纯 N-磺酰氨基醇及其共聚物作为高对映选择性烯丙基硼化反应的手性助剂”反应性和功能性聚合物 (1998)。
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    0
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ITSUNO Shinichi其他文献

ITSUNO Shinichi的其他文献

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{{ truncateString('ITSUNO Shinichi', 18)}}的其他基金

Synthesis of chiral ionic polymers and their application to asymmetric catalysis
手性离子聚合物的合成及其在不对称催化中的应用
  • 批准号:
    23350053
  • 财政年份:
    2011
  • 资助金额:
    $ 1.98万
  • 项目类别:
    Grant-in-Aid for Scientific Research (B)
Synthesis of chiral quaternary ammonium polymers and their application to asymmetric reaction
手性季铵聚合物的合成及其在不对称反应中的应用
  • 批准号:
    19550122
  • 财政年份:
    2007
  • 资助金额:
    $ 1.98万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
ASYMMETRIC CATALYST DERIVED FROM POLYMER IMOBILIZED CHIRAL 1,2-DIAMINES
源自聚合物固定化手性 1,2-二胺的不对称催化剂
  • 批准号:
    15550089
  • 财政年份:
    2003
  • 资助金额:
    $ 1.98万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
ASYMMETRIC SYNTHESIS OF OPTICALLY ACTIVE POLYMERS HAVING MAIN CHAIN CHIRALITY
具有主链手性的光学活性聚合物的不对称合成
  • 批准号:
    13650933
  • 财政年份:
    2001
  • 资助金额:
    $ 1.98万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
Asymmetric polymerization using chirally modified Lewis acid
使用手性改性路易斯酸的不对称聚合
  • 批准号:
    11650907
  • 财政年份:
    1999
  • 资助金额:
    $ 1.98万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
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