New Syntheses of Highly Reactive and Functional Organometallic Compounds and its Application to Organic Syntheses

本研究项目取得了以下成果：带有氨基的乙烯基硅烷的酸催化环化反应。吡咯烷的立体选择性合成在酸性催化剂存在下，带有吸电子基团保护的氨基的乙烯基硅烷顺利地被氧化成2-（硅甲基）吡咯烷。用烯丙基锡烷进行的1-6-烯炔自由基环化反应和以烯醇化锡为自由基转移剂的新自由基反应在AEBN存在下，β-位带有自由基稳定基团的烯丙基三丁基锡烷与1，6-烯炔的环化反应，得到了具有锡烷基和烯丙基的环化产物，产率中等至良好。该环化反应对于合成高度官能化的五元碳环和杂环是有价值的。4.3. ...更多信息 0]壬-l-烯沿着与单环化产物。α-卤代酯、α-腈和α-酮与烯醇化锡的自由基加成反应，中高产率地得到相应的γ-酮衍生物。这种均裂过程被应用到三组分之间的偶联反应的锡烯醇化物，卤代烷，和缺电子的alkenes.Silicon-directed环化反应的乙烯基硅烷：立体选择性合成四氢呋喃和四氢吡喃Silicon-directed立体选择性synaddition羟基到烯双键发生在分子内的酸催化环化反应的乙烯基硅烷轴承羟基。环化通过羟基的立体定向合成加成进行。乙烯基硅烷，在亚甲基系链上带有取代基的（Z）-5-甲硅烷基-4-戊烯-1-醇，顺利地进行酸催化环化，分别得到反式-2，5-、顺式-2，4-和反式-2，3-二取代的四氢呋喃，具有中等至高的立体选择性。三烷基锰（II）酸盐试剂“RMnLi”与碘甲基硫化物反应生成硫甲基锰试剂，其中三烷基锰用作还原剂而不是烷基化剂。三烷基锰试剂的还原行为为直接生成一类结构多样的新试剂--硫甲基锰试剂提供了一种途径，所生成的硫甲基锰试剂与烯丙基溴、烯酮和醛反应。使用铜（I）盐催化的乙硅烷的β-烯酮乙硅烷与Cu（I）盐的反应有效地诱导Si-Si键的断裂以在非质子极性溶剂中生成甲硅烷基亲核试剂，发现在催化量的铜（I）盐的作用下，与α，β-不饱和烯酮的4-加成反应顺利进行。该反应成功应用于六甲基二硅烷，生成迄今为止不容易获得的三甲基硅烷基亲核试剂。前所未有的锰介导反应：不稳定羰基叶立德的生成。活性锰从双（氯甲基）醚作为前体，并使用该体系与锰作为还原剂，叶立德与缺电子亲偶极试剂的反应可以在不直接用还原剂还原亲偶极试剂的情况下实现。少

The following results are obtained in this research project.Acid-Catalyzed Cyclization ofVinylsilanes Bearing an Amino Group. Stereoselective Synthesis ofPyrrolidinesIn the presence of an acid catalyst, vinylsilanes bearing an amino group protected by an electron-withdrawing group were smoothly bychzed to 2-(silylmethyl) pyrrolidines. This cyclization was utilized for the Stereoselective synthesis of 2 ndisubstituted pyrrqlidines (n = 3-5).Radical Cyclization of 1-6-Enynes Using Allylstannanes and New Radical Reactions Using Stannyl Enolates as Radical Transfer AgentsIn the presence of AEBN, allyltributylstannanes bearing a radical-stabilizing group at the β-position smoothly reacted with 1,6-enynes to give cyclized products incorporated with the stannyl and allyl groups in moderate to good yields This cyclization is valuable for the synthesis of highly functionalized 5-membered carbocycles and heterocycles The reactions with β-cyanoallylstannane formed a certain amount of bicyclo[4.3. … More 0]non-l-enes along with monocyclized products. The radicaHmtiated reactions of α-halo-esters, -nitriles, and -ketones with stannyl enolates gave the corresponding γ-keto denvatives in moderate to high yields. This homolytic process was applied to the three-component coupling reaction among stannyl enolates, haloalkanes, and electron-deficient alkenes.Silicon-directed Cyclization of Vinylysilanes : Stereoselective Synthesis of Tetrahydrofurans and TetrahydropyransSilicon-directed Stereoselective syn addition of hydroxy group to olefmic double bond occurs intramolecularly in an acid-catalyzed cyclization of vinylsilanes bearing hydroxy group. The cyclization proceeds by stereospecific syn addition of the hydroxy group Vinylsilanes, (Z)-5-silyl-4-penten-l-ols bearing a substituent on the methylene tether, smoothly undergo the acid-catalyzed cyclization to give trans-2,5-, cis-2,4-, and trans-2,3-disubstituted tetrahydrofurans respectively, with moderate to high stereoselectivitv.Manganese Ate Species: Generation,and Reactions with ElectrophilesTrialkylmanganese (II) ate reagents, "RMnLi" reacted with iodomethylsulfides to produce thiomethylmanganese reagents, where the manganate serves as a reductant not an alkylation agent. The reductive behavior of trialkylmanganese (II) ate reagents provides a protocol for the direct generation of a new class of reagents thiomethylmanganese reagents with structural variety, and the generated thiomethylmanganese reagents reacted with allyl bromides, enones and aldehydes.New Method for Introduction of a Silyl Group into α,β-Enones Using a Disilane Catalyzed by a Copper(I) salt.The reaction of a disilane with a Cu(I) salt efficiently induces cleavage of the Si-Si bond to generate a silyl nucleophile in aprotic polar solvent and its 1,4-addition to α,β-unsaturated enones smoothly proceeds with a catalytic amount of a Cu(I) salt were found. This reaction is successfully applied to hexamethyldisilane to generate a trimethylsilyl nucleophile hitherto not easily accessible.Unprecedented Manganese-Mediated Reactions : Generation of Non-Stabilized Carbonyl Ylids.Activated manganese generates nonstabilized carbonyl ylides from bis (chloromethyl) ethers as a precursor, and using this system with manganese as a reductant, the reactions of the ylides with electron-deficient dipolarophiles can be attained without the direct reduction of dipolarophiles by the reductant. Less