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: 10450334
• 负责人: HOSOMI Akira
• 金额: $ 9.09万
• 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: 1998
• 资助国家: 日本
• 起止时间: 1998 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-10450334/
• 关键词: Si-Cu exchange reaction; Stereoselective synthesis; Carbonyl ylides; Silicon-directed cyclization; Srereocontrol; Samarium-mediated reactions; [3+2] Cycloaddition; O- and N-Containing heterocycles; 高配位マンガンアート反応剤; 1,3-双極子反応剤; 還元的メタル化反応; 5配位ケイ素ヒド

The following results are obtained in this research project.1. Silicon-directed Cyclization of Vinylysilanes : Stereoselective Synthesis of Tetrahydrofurans and TetrahydropyransSilicon-directed stereoselective syn addition of hydroxy group to olefinic 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-1-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 stereoselectivity.2. Acid-Catalyzed Cyclization of Vinylsilanes Bearing an Amino Group. Stereoselective Synthesis of PyrrolidinesIn the presence of an acid catalyst, vinylsilanes bearing an amino group protected by an electron-withdrawing group were smoothly cyclized to 2-(silylmethyl) pyrrolidines. This cyclizat … More ion was utilized for the stereoselective synthesis of 2, n-disubstituted pyrrolidines (n=3-5).3. Unprecedented Manganese-Mediated Reactions : Generation of Non-Stabilized Carbonyl YlidsActivated 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.4. Manganese Ate Species : Generation and Reactions with ElectrophilesTrialkylmanganese (II) ate reagents, "R_3MnLi" 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 aprotocol 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.5. Radical Cyclization of 1,6-Enynes Using Allylstannanes and New Radical Reactions Using Stannyl Enolates as Radical Transfer AgentsIn the presence of AIBN, 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 [4.3.0] non-1-enes along with monocyclized products. The radical-initiated reactions of α-halo-esters, -nitriles, and -ketones with stannyl enolates gave the corresponding γ-keto derivatives in moderate to high yields. This homolytic process was applied to the three-component coupling reaction among stannyl enolates, haloalkanes, and electron-deficient alkenes.6. 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 an 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. Less

在本研究项目中获得了以下结果：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立体选择性合成烯烃双键羟基加成发生在含羟基乙烯基硅烷的酸催化环化过程中。环化是通过羟基的立体定向同步加成进行的。乙烯基硅烷(Z)-5-硅基-4-戊烯-1-醇，在亚甲基系醚上有一个取代基，能顺利地进行酸催化环化反应，分别生成反式-2,5-、顺式-2,4-和反式-2,3-二取代四氢呋喃，具有中等至高的立体选择性。含氨基乙烯基硅烷的酸催化环化。立体选择性合成吡咯烷在酸性催化剂的作用下，乙烯基硅烷的一个氨基被一个吸电子基团保护，它被顺利地环化成2-（硅甲基）吡咯烷。该环化反应被用于立体选择性合成2，n -二取代吡咯烷（n=3-5）。史无前例的锰介导反应：非稳定羰基基基化合物的生成活性锰以双（氯甲基）醚为前体生成非稳定羰基基化合物，使用锰作为还原剂的该体系，可以在不直接还原亲偶极试剂的情况下实现与缺电子亲和试剂的羰基基化合物的反应。锰酸盐种类：与亲电烷基锰酸盐试剂的生成和反应，“R_3MnLi”与碘甲基硫化物反应生成硫甲基锰试剂，其中锰酸盐作为还原剂而不是烷基化剂。三烷基锰（II）酸盐试剂的还原行为为直接生成一类新的试剂提供了一种方案，即具有不同结构的硫甲基锰试剂，所生成的硫甲基锰试剂可与烯丙基溴、烯酮和醛反应。以烯丙基锡烷为自由基转移剂的1,6-炔的自由基环化反应和以斯坦烯醇酯为自由基转移剂的新自由基反应在AIBN的存在下，在β-位置有一个自由基稳定基团的烯丙基三丁基锡烷与1,6-炔顺利反应，得到含锡基和烯丙基的环化产物，收率中等至较高。这种环化对于合成高官能化的5元碳环和杂环具有重要意义。与β-氰丙基锡烷反应生成一定量的双环[4.3.0]非1-烯，并生成单环化产物。α-卤化酯、-腈和-酮与烯醇化斯坦烯醇酯的自由基引发反应得到相应的中高产γ-酮衍生物。将此均解过程应用于烯醇化、卤代烷和缺电子烯烃之间的三组分偶联反应。用铜(I)盐催化二硅烷在α， β-烯酮中引入硅基的新方法。二硅烷与Cu (I)盐在非质子极性溶剂中有效地诱导Si-Si键断裂生成硅基亲核试剂，并且在Cu (I)盐的催化量下，其对α， β-不饱和烯酮的1,4加成反应顺利进行。该反应成功地应用于六甲基二硅烷，生成三甲基硅基亲核试剂，迄今为止不容易获得。少

项目成果

Hajime Ito, Tomoko Ishizuka, Jun-ichi Tateiwa, Motohiro Sonoda, and Akira Hosomi: "New Method for Introduction of a Silyl Group into α,β-Unsaturated Carbonyl Compounds Using a Disilane Catalyzed by a Copper(I) Salt"J. Am. Chem. Soc.. 120(43). 11196-11197

Hajime Ito、Tomoko Ishizuka、Jun-ichi Tateiwa、Motohiro Sonoda 和 Akira Hosomi：“使用铜 (I) 盐催化的乙硅烷将甲硅烷基引入 α,β-不饱和羰基化合物的新方法”J.化学。120(43)。

A.Hosomi: "Selective O-Acylation of Silyl Enol Ethers with Acid Halides Mediated by a Copper(I) Salt" Tetrahedron Lett.39・35. 6295-6298 (1998)

A.Hosomi：“铜（I）盐介导的甲硅烷基烯醇醚与酰基卤的选择性O-酰化”Tetrahedron Lett.39・35（1998）。

A.Hosomi: "Allsiliylation of Carbon-Carbon and Carbon-Oxygen Unsaturated Bonds via a Radical Process" J.Org.Chem.63・17. 5740-5741 (1998)

A.Hosomi：“通过自由基过程进行碳-碳和碳-氧不饱和键的全甲硅烷基化”J.Org.Chem.63・17（1998）。

Hajime Ito and Akira Hosomi: "New Synthetic Reactions Using Group 11 Metal Compounds as a Catalyst"J. Synth. Org. Chem., Japan. 58(4). 274-284 (2000)

Hajime Ito 和 Akira Hosomi：“使用 11 族金属化合物作为催化剂的新合成反应”J。

A.Hosomi: ""Silicon (IV) Reagents" in Lewis Acid Reagents: A Practical Approach (The Practical Approach in Chemistry Series)."Oxford Science Publications. 270 (1999)

A.Hosomi：“路易斯酸试剂中的“硅（IV）试剂”：实用方法（化学系列中的实用方法）。”牛津科学出版物。