Solid-Phase Synthesis of Chiral Silicon-Based Reagents and Their Application to Organic Synthesis

手性硅基试剂的固相合成及其在有机合成中的应用

基本信息

批准号：
14205126
负责人：
SUGINOME Michinori
金额：
$ 27.62万
依托单位：
Kyoto University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (A)
财政年份：
2002
资助国家：
日本
起止时间：
2002 至 2004
项目状态：
已结题

项目摘要

New synthetic intermediates and reagents for organic synthesis have been developed in response to the demands for the efficient construction of large chemical libraries consisting of optically active organic molecules. The results of this research projects are summarized below.(1)Polymer-bound optically active allylsilanes were synthesized via palladium-catalyzed solid-phase intramolecular bis-silylation of optically active allylic alcohols. Thus obtained allylsilanes were found to react with electrophiles, giving highly enantioenriched alcohols and cyclic ethers stereoselectively.(2)Silylboranes react with various unsaturated organic molecules including vinylcyclopropane and terminal allenes, leading to the synthesis of new organic molecules that contain silicon and boron. Enantioface-selective silaboration of terminal allenes has been developed by using chiral phosphine ligands with palladium complexes, affording enantio-enriched 2-borylallysilanes efficiently, which serve as new 2-b … More orylallyllation reagents for the synthesis of functionalized organoboron compounds.(3)Cyanoboranes were found to add to carbon-carbon triple bonds in the presence of palladium catalysts. The reaction provides a unique access to 2-borlyacrylonitriles, which serves as convenient reagents for the synthesis of highly substituted α,β-unsaturated nitriles.(4)Aminoboranes serve as new iminium ion generators in organic synthesis. The reagent allows to avoid acidic reaction conditions, which are usually required for the amination reactions that proceed via the formation of iminium ion intermediates. Strecker reaction, Mannich reaction and reductive amination reactions proceed in the presence of aldehydes, nucleophiles, and aminoboranes under non-acidic reaction conditions.(5)As a related research project, a new screw-sense selective polymerization reaction has been developed Polymerrization of 1,2-diisocyanobenzen derivatives proceeded with optically active arylpalladium(II) complexes, leading to the formation of optically active poly(quinoxaline-2,3-diyl)s. The selectivity reaches >90% screw-sense excesses when structurally well-tuned chiral organopalladium initiators were used. Less

为了响应有效构建由光学活性有机分子组成的大型化学文库的需求，已开发出新的有机合成合成中间体和试剂。该研究项目的结果总结了下面。（1）通过钯催化的光学活性烯丙基醇的分子内二酰基化合物合成聚合物的光学活性烯丙基硅烷。发现获得的Allylsilanes与电物质反应，立体选择性地提供了高度映射的醇和环状以醚。 Enantioface-selective silicon allens has been developed by using chiral phosphine ligands with palladium complexes, affording enantio-enriched 2-borylallysilanes efficiently, which serve as new 2-b … More oryllallyllation reagents for the synthesis of functionalized organoboron compounds.(3)Cyanoboranes were found to add to carbon-carbon triple bonds in the钯催化剂的存在。该反应提供了对2-乙丙丙酰丙烯硝基硝酸盐的独特访问，该试剂可作为合成高度取代的α，β-不饱和硝酸盐的方便试剂。（4）胺在有机合成中用作新的iminium离子发电机。该试剂允许避免酸性反应条件，这通常是通过形成亚米尼离子中间体进行的分析反应所必需的。在非酸性反应条件下，在存在醛，核恐惧症和氨基烷的存在下，Strecker反应，Mannich反应和减少了胺化反应进行。（5）作为一个相关的研究项目，新的螺丝透度选择性聚合反应已开发出1,2-二甲基化造成效应的组合效应（均具有1,2-二异基因的复合体），该反应是由1,2-二异基因造成的（均为II）的组合作用（光学活性聚（quinoxalline-2,3-二烯基）s。当使用结构良好的手性有机丙达旦发起人时，选择性达到了90％的螺丝固定。较少的