Development of Allylic Boron Reagents

烯丙基硼试剂的研制

基本信息

  • 批准号:
    12650842
  • 负责人:
  • 金额:
    $ 2.05万
  • 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:
    2000
  • 资助国家:
    日本
  • 起止时间:
    2000 至 2001
  • 项目状态:
    已结题

项目摘要

1. Nucleophilic Borylation Reactions of Allylic Electrophiles with Diborons(1) Nucleophilic borylation reactions of allylic acetates or halides with bis(pinacolato)diboron regio-and stereoselectively proceeded at 50 degree when using a combination of Pd(dba)2/DMSO or Pd(dba)2-2AsPh3/KOAc/toluene to afford allylic boron compounds in excellent yields. The reactions also tolerated various functionalities such as carbonyl groups. A catalytic cycle may involve oxidative addition of the allylic electrophile to a palladium(0) complex, transmetalation between the diboron and a palladium(II) intermediate, and reductive elimination of the allylic boron compound.(2) Three-component reactions of bis(pinacolato)diboron, allylic acetates, and aldehydes smoothly occurred under the conditions optimized above (Pd(dba)2/DMSO/50 degree), resulting in high yields of acyclic homoallylic alcohols. Sequential reactions, involving nucleophilic borylation of allylic acetates substituted by a carbonyl group in the presence of a Pd(dba)2-2AsPh3 catalyst in toluene at 50 degree and intramolecular allylboration at 100 degree provided cyclic homoallylic alcohols in high yields with high cis-stereoselectivity.2. Synthesis of Allylic Boron Compounds via Transition Metal-Catalyzed Isomerization Reactions of 3-Alkoxyvinylboranes(1) Isomerization reactions of 3-alkoxyvinylboranes stereoselectively proceeded in the presence of [Ir(COD)(PPh2Me)2]PF6 and NiC12(PPh2Me)2 catalyst to give E- and Z-allylic boron compounds, respectively.(2) 3-Alkoxyvinylboranes having a carbonyl functionality underwent the catalytic isomerization followed by intramolecular allylboration to give cyclic ethers in good yields.
1.烯丙基亲电试剂与二硼的亲核硼化反应(1)在Pd(dba)_2/DMSO或Pd(dba)_2 - 2AsPh_3/KOAc/甲苯的混合体系中,烯丙基乙酸酯或卤代物与二硼频哪醇酯的亲核硼化反应在50 ℃下区域和立体选择性地进行,得到了高产率的烯丙基硼化合物。该反应还容许各种官能团,如羰基。催化循环可涉及烯丙基亲电试剂与钯(0)络合物的氧化加成、二硼和钯(II)中间体之间的金属转移和烯丙基硼化合物的还原消除。(2)在上述优化条件下(Pd(dba)2/DMSO/50 ℃),双(频哪醇合)二硼、乙酸烯丙酯和醛的三组分反应顺利进行,得到高产率的无环高烯丙醇。在Pd(dba)2- 2AsPh 3催化剂存在下,羰基取代的烯丙基乙酸酯在甲苯中于50 ℃发生亲核硼化反应,然后在100 ℃发生分子内烯丙基硼化反应,以高产率和高顺式立体选择性合成了环状高烯丙醇。过渡金属催化的3-烷氧基乙烯基硼烷异构化反应合成烯丙基硼化合物(1)在[Ir(COD)(PPh_2Me)_2] PF_6和NiCl_2(PPh_2Me)_2催化下,3-烷氧基乙烯基硼烷的异构化反应立体选择性地分别得到E-和Z-烯丙基硼化合物。(2)具有羰基官能团的3-烷氧基乙烯基硼烷经催化异构化和分子内烯丙基硼化反应,以较好的产率得到环醚。

项目成果

期刊论文数量(33)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
Tatsuo Ishiyama : "A Heck-Type Reaction Involving Carbon-Heteroatom Double Bonds. Rhodium (I)-Catalyzed Coupling of Ary1 Halides with N-Pyrazyl Aldimines"J.Am.Chem.Soc.. 122. 12043-12044 (2000)
Tatsuo Ishiyama :“涉及碳-杂原子双键的 Heck 型反应。铑 (I) 催化芳基卤化物与 N-吡嗪基醛亚胺的偶联”J.Am.Chem.Soc.. 122. 12043-12044 (2000)
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    0
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Yasunori Yamamoto: "Stereoselective Isomerization of Unsymmetrical Diallyl Ethers to Allyl(E)-Vinyl Ethers by a Cationic Iridium Catalyst"Synth. Commun.. 30. 2383-2391 (2000)
Yasunori Yamamoto:“通过阳离子铱催化剂将不对称二烯丙基醚立体选择性异构化为烯丙基(E)-乙烯基醚”合成。
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    0
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Tatsuo Ishiyama : "Chemistry of Group 13 Element-Transition Metal Linkage - The Platinum- and Palladium-Catalyzed Reactions of (Alkoxo) diborons"J.Organomet.Chem.. 611. 392-402 (2000)
Tatsuo Ishiyama :“第 13 族元素-过渡金属键合的化学 - (Alkoxo) 二硼的铂和钯催化反应”J.Organomet.Chem.. 611. 392-402 (2000)
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    0
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  • 通讯作者:
Kou Takahashi: "Synthesis of 1-Alkenylboronic Esters via Palladium-Catalyzed Cross-Coupling Reaction of Bis(pinacolato)diboron with 1-Alkenyl Halides and Triflates"Chem. Lett.. 126-127 (2000)
Kou Takahashi:“通过钯催化双(频哪醇)二硼与 1-烯基卤化物和三氟甲磺酸酯的交叉偶联反应合成 1-烯基硼酸酯”Chem.
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    0
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Tatsuo Ishiyama: "A Heck-Type Reaction Involving Carbon-Heteroatom Double Bonds.Rhodium(I)-Catalyzed Coupling of Aryl Halides with N-Pyrazyl Aldimines"J. Am. Chem. Soc.. 122. 12043-12044 (2000)
Tatsuo Ishiyama:“涉及碳-杂原子双键的 Heck 型反应。铑 (I) 催化芳基卤化物与 N-吡嗪基醛亚胺的偶联”J。
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    0
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ISHIYAMA Tatsuo其他文献

ISHIYAMA Tatsuo的其他文献

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{{ truncateString('ISHIYAMA Tatsuo', 18)}}的其他基金

Development of Highly Efficient Synthesis of Organoboron Compounds
有机硼化合物高效合成研究进展
  • 批准号:
    21350049
  • 财政年份:
    2009
  • 资助金额:
    $ 2.05万
  • 项目类别:
    Grant-in-Aid for Scientific Research (B)
INTRODUCTION OF BORYL OR SILYL GROUPS VIA AROMATIC OR ALIPHATIC CARBON-HYDROGEN BOND ACTIVATION
通过芳香族或脂肪族碳氢键活化引入硼基或甲硅烷基
  • 批准号:
    17065001
  • 财政年份:
    2005
  • 资助金额:
    $ 2.05万
  • 项目类别:
    Grant-in-Aid for Scientific Research on Priority Areas
Developments of Direct Synthesis and New Catalytic Reactions of Aromatic Boron Compounds
芳香硼化合物的直接合成及新型催化反应研究进展
  • 批准号:
    16550089
  • 财政年份:
    2004
  • 资助金额:
    $ 2.05万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
Highly Efficient Synthesis of Vinylboron Compounds via Transition Metal Catalyst/Diboron System
通过过渡金属催化剂/二硼体系高效合成乙烯基硼化合物
  • 批准号:
    14550815
  • 财政年份:
    2002
  • 资助金额:
    $ 2.05万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)

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