New Reactions Using Highly Functional Organometallic Compounds and its Application to Synthetic Chemistry

本研究取得了以下成果：1.乙烯基硅烷的硅导向环化反应：四氢呋喃和四氢吡喃的立体选择性合成在含羟基的乙烯基硅烷的酸催化环化反应中，羟基与烯双键的硅导向立体选择性合成是在分子内进行的。因此，5-二甲基苯基甲硅烷基-4-戊烯-1-醇被顺利环化为2-在催化量的对甲苯磺酸（TsOH）或TiCl_4的处理下，（二甲基苯基甲硅烷基）甲基四氢呋喃。非稳定羰基叶立德的产生钐显示出强还原能力，并且凭借这种特性连同其亲氧性，广泛应用于有机合成中碳-碳键的形成和各种官能团的高选择性转化。在我们对活性物种的产生和反应的研究过程中，我们报告了他 ...更多信息 控制新的活性物种的产生，非稳定的羰基叶立德从碘甲基甲硅烷基醚介导的钐，否则难以获得，和它们的[3+2]环加成到各种不饱和化合物，如醛，烯烃，联烯，和炔。四丁基锰配合物'Bu_4MnLi_2'与烯丙基和丙-2-烯丙基的反应炔基溴化以产生相应的烯丙基-和丙-2-炔基-锰物质，其进一步与亲电试剂如醛、酮、环氧化物和氯硅烷反应以高产率提供相应的烯丙基化和丙-2-炔基化和/或联烯基化产物。4.通过自由基方法的炔和烯的烯丙基锡烷基化：二、三取代乙烯基锡烷的立体选择性合成在AIBN存在下，β位带有吸电子基团的烯丙基锡烷容易与末端和缺电子内炔反应，以中等至良好的产率得到β-烯丙基取代乙烯基锡烷。烯丙基甲锡烷基化只进行反加成反应。在β-位带有吸电子基团的烯丙基锡烷容易与各种缺电子烯烃反应以引入烯丙基和锡烷基。少

The following results are obtained in this research project.1.Silicon-directed Cyclization of Vinylysilanes : Stereoselective Synthesis of Tetrahydrofuranes and TetrahydropyranesSilicon-directed stereoselective syn addition of hydroxy group to olefinic double bond occurs intramolecularly in an acid-catalyzed cyclization of vinylsilanes bearing hydroxy group. Thus 5-dimethylphenylsilyl-4-penten-1-ol is smoothly cyclized to 2- (dimethylphenylsilyl) methyltetrahydrofuran upon the treatment of a catalytic amount of p-toluenesulfonic acid (TsOH) or TiCl_4.2.Unprecedented Samarium-Mediated Reactions : Generation of Non-Stabilized Carbonyl YlidsSamarium reveals a strong reducing ability and by virtue of this character together with its oxophilicity, is widely applied to organic synthesis in the formation of carbon-carbon bonds and transformation of a variety of functionalities with high selectivities. In the course of our study on the generation and reactions of reactive species, we report he … More rein the generation of novel active species, non-stabilized carbonyl ylids from iodomethyl silyl ethers mediated by samarium, otherwise inaccessible, and their [3+2] cycloadditions to a variety of unsaturated compounds such as aldehydes, alkenes, allenes, and alkynes.3.Manganese AteSpecies : Generation and Reactions with ElectrophilesTetrabutylmanganese ate complex 'Bu_4MnLi_2' reacts with allylic and prop-2-ynylic bromides to generate the corresponding allyl-and prop-2-ynyl-manganese species which further react with electrophiles such as aldehydes, ketones, epoxide, and chlorosilanes to afford the corresponding allylated and prop-2-ynylated and/or allenylated products in high yields.4.Allylstannylation of Alkynes and Alkenes via a Radical Process : Stereoselective Synthesis of Di-and Tri-Substituted VinylstannanesIn the presence of AIBN,allylstannanes bearing an electron-withdrawing group at the beta-position easily reacted with terminal and electron-deficient internal alkynes to give beta-allyl-substituted vinylstannanes in moderate to good yields. The allylstannylation proceeds with anti addition exclusively. Allylstannanes bearing an electron-withdrawing group at the beta-position easily reacted with various electron-deficient alkenes to introduce both the allyl and stannyl groups. Less