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

为了满足高效构建由光学活性有机分子组成的大型化学库的需求，开发了新的有机合成中间体和试剂。本研究项目的结果总结如下：（1）聚合物结合的光学活性烯丙基硅烷。通过钯催化的光学活性烯丙醇的高度固相分子内双硅烷化合成，发现由此获得的烯丙基硅烷与亲电子试剂反应，得到。 (2)甲硅烷基硼烷与乙烯基环丙烷和末端丙二烯等各种不饱和有机分子反应，利用手性技术开发了含硅和硼的新型有机分子的对映体选择性硅化反应。膦配体与钯配合物，有效提供对映体富集的2-硼基烯丙基硅烷，它可作为新型 2-b … More 烯丙基化试剂，用于合成官能化有机硼化合物。(3)氰基硼烷被发现在钯催化剂存在下加成到碳-碳三键上，该反应提供了获得 2-硼基丙烯腈的独特途径。，可作为合成高取代α,β-不饱和腈的便捷试剂。(4)氨基硼烷作为新的亚胺离子该试剂可以避免酸性反应条件，而酸性反应条件通常是通过形成亚胺离子中间体进行的胺化反应、曼尼希反应和还原胺化反应在醛、亲核试剂存在下进行的。 (5)作为相关研究项目，开发了一种新型螺杆选择性聚合反应。 1,2-二异氰基苯衍生物与光学活性芳基钯(II)配合物反应，形成光学活性聚(喹喔啉-2,3-二基)，当结构调整良好时，选择性达到 > 90% 的螺旋感应过量。手性有机钯引发剂用量较少。