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

高活性、功能性有机金属化合物的新合成及其在有机合成中的应用

• 批准号: 11554029
• 负责人: HOSOMI Akira
• 金额: $ 9.02万
• 依托单位: University of Tsukuba
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-11554029/
• 关键词: Si-Cu exchange reaction; Stereoselective synthesis; Carbonyl ylides; Srereocontrol; Samarium-mediated reactions; [3+2] Cycloaddition; O- and N-Containing heterocycles; プロパルギルマンガンアート錯体; 還元的メタル化反応; 5配位ケイ素ヒドリド反応剤

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

本研究项目取得了以下成果：含氨基乙烯基硅烷的酸催化环化。吡咯烷的立体选择性合成在酸催化剂存在下，带有吸电子基团保护的氨基的乙烯基硅烷顺利地缩合成2-(甲硅烷基甲基)吡咯烷。该环化用于立体选择性合成 2 个二取代吡啶（n = 3-5）。使用烯丙基锡烷进行 1-6-烯炔的自由基环化和使用锡烷基烯醇化物作为自由基转移剂的新自由基反应在 AEBN 存在下，烯丙基三丁基锡烷在 β-位与1,6-烯炔顺利反应，以中等至良好的产率得到与甲锡烷基和烯丙基结合的环化产物。这种环化对于合成高功能化的5元碳环和杂环很有价值。与β-氰基烯丙基锡烷反应形成一定量的双环[4.3。 … 更多 0]非-l-烯以及单环化产品。 α-卤代酯、α-腈和-酮与甲锡烷基烯醇化物的自由基反应以中等至高产率生成相应的γ-酮衍生物。该均裂过程应用于甲锡烷基烯醇化物、卤代烷烃和缺电子烯烃之间的三组分偶联反应。乙烯基硅烷的硅定向环化：四氢呋喃和四氢吡喃的立体选择性合成硅定向羟基与烯属双烯的立体选择性顺加成 键在带有羟基的乙烯基硅烷的酸催化环化反应中在分子内发生。环化通过羟基的立体定向顺式加成进行乙烯基硅烷，在亚甲基链上带有取代基的(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，具有中等到高的产率。 立体选择性。锰酸种类：生成以及与亲电子试剂的反应三烷基锰(II)酸试剂“RMnLi”与碘甲基硫反应生成硫代甲基锰试剂，其中锰酸盐充当还原剂而不是烷基化剂。三烷基锰（II）试剂的还原行为为直接生成结构多样的新型试剂硫代甲基锰试剂提供了方案，并且生成的硫代甲基锰试剂与烯丙基溴、烯酮和醛反应。利用乙硅烷催化将甲硅烷基引入α,β-烯酮的新方法 在非质子极性溶剂中，乙硅烷与 Cu(I) 盐的反应有效地诱导 Si-Si 键断裂，生成甲硅烷基亲核试剂，并且发现其与 α,β-不饱和烯酮的 1,4-加成反应在催化量的 Cu(I) 盐的情况下顺利进行。该反应成功应用于六甲基二硅烷，生成迄今为止不易获得的三甲基甲硅烷基亲核试剂。前所未有的锰介导反应：生成不稳定的羰基叶立德。活化的锰以双（氯甲基）醚为前体，生成不稳定的羰基叶立德，并使用该系统以锰为原料 如果使用还原剂，叶立德与缺电子亲偶极体的反应可以在不通过还原剂直接还原亲偶极体的情况下实现。较少的

项目成果

A.Hosomi: "Non-Stabilized Carbonyl Ylides for α-Iodo Silyl Ethers : A Practical Approach (The Practical Approach in Chemistry Series)"Oxford Science Publications. 270 (2000)

A.Hosomi：“α-碘代甲硅烷基醚的非稳定羰基叶立德：实用方法（化学系列中的实用方法）”牛津科学出版物 270（2000）。

Makoto Hojo, Kyosuke Sakata, Nobuo Ushioda, Takeshi Watanabe, Hisashi Nishikon, Akira Hosomi: "Reductive Generation of Enolates Using Chromium(III) Ate-Type Reagent as a Reductant and Reactions of the Enolates with Electrophiles"Organometallics. 20 (24).

Makoto Hojo、Kyosuke Sakata、Nobuo Ushioda、Takeshi Watanabe、Hisashi Nishikon、Akira Hosomi：“使用铬(III) Ate型试剂作为还原剂还原烯醇化物以及烯醇化物与亲电子试剂的反应”有机金属。

Makoto Hojo, Rie Sakuragi, Satoru Okabe, Akira Hosomi: "Allyl- and Propargylchromium Reagents Generated by a Chromiuman) Ate-type Reagent as a Reductant and their Reactions with Electrophiles"Chem. Commun.. (4). 357-358 (2001)

Makoto Hojo、Rie Sakuragi、Satoru Okabe、Akira Hosomi：“由铬满）Ate 型试剂作为还原剂生成的烯丙基和炔丙基铬试剂及其与亲电试剂的反应”Chem。

Jun-ichi Tateiwa, Akira Hosomi: "Pentacoordinate Organosilicate-Catalyzed Michael Addition of p-Keto Ester to 3-Buten-2-one"European J. Org. Chem.. 4 (8). 1445-1448 (2001)

Jun-ichi Tateiwa，Akira Hosomi：“五配位有机硅酸盐催化对酮酯到 3-丁烯-2-酮的迈克尔加成”European J. Org。

A. Hosomi: "Pentacoordinate Organosilicate-Catalyzed Michael Addition of b-Keto Ester to 3-Buten-2-one"European J. Org. Chem. 4・8. 1445-1448 (2001)

A. Hosomi：“b-酮酯与 3-丁烯-2-酮的五配位有机硅酸盐催化迈克尔加成”European J. Org. 1445-1448 (2001)。