Molecular Design for Creation of Synthetic Equivalents and Reseach Development for the Application to Organic Synthesis

用于创建合成等效物的分子设计和有机合成应用的研究开发

• 批准号: 05554022
• 负责人: HOSOMI Akira
• 金额: $ 3.52万
• 依托单位: University of Tsukuba
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Developmental Scientific Research (B)
• 财政年份: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1994
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-05554022/
• 关键词: Di-exo-methylene compound; Fused isoxazoles; [4+2] Cycloaddition; [2+2] Cycloaddition; 1,2,3-Butatriene; 1,3-Elimination; 1,3-Dipolar reagent; [3+2] Cycloaddition; 立体特異的合成; テトラヒドロフラン; 有機ケイ素化合物; 高選択的有機合成; ジ-エキソ-メチレン化合物; 1,4-脱離反応; (トリメチルシリルメチル

1.Synthesis of new di-exo-methylene compounds and fused isoxazolesWe have prepared and used methyl (trimethylsilylmethyl) acetylenecarboxylate as a dipolarophile and a common key compound leading to precursors for di-exo-methylene compounds which subsequently react with olefins in [4+2] cycloaddition mode to afford fused heterocyclic compounds. We found a new and general route toward the synthesis of the precursor for di-exo-methyleneisoxazolines and their Diels-Alder reactions leading to fused isoxazoles.2.New access to di-exo-methylenecyclobutanes via [2+2] cycloaddition of 3-methylthio-4-trimethylsilyl-1,2-butadiene with alkenes mediated by a Lewis acidIn the course of studies in organic synthesis using allylsilanes and propargylsilanes, we found a new and general route toward the synthesis of di-exo methylenecyclobutanes via the [2+2] cycloaddition of 3-methylthio-4-trimethylsilyl-1,2-butadiene with alkenes promoted by a Lewis acid followed by sequential reactions to sulfones by oxidation and 1,2-elimination. Di-exo-methylenecyclobutanes were also successfully applied to construct a bicyclo [5.2.0] nonane ring system by the [4+3] cycloaddition with an 2-oxyallyl cation. The title compound can be viewed formally as a synthetic equivalent of 1,2,3-butatriene or 1,3-butadien-2,3-diyl.3.Creation and Reactions of Carbonyl Ylides and Related 1,3-Dipolar Reagents1,3-Dipolar reagents are important and interesting chemical species from both synthetic and theoretical points of view. We found that the novel findings that simple carbonyl ylides, otherwise inaccessible, were indeed expediently generated by the silicon-based 1,3-elimination from alpha-aryl-substituted chloromethyl trimethylsilylmethyl ether under mild and neutral conditions which provided the powerful one-step synthesis of dihydrofurans and tetrahydrofurans and related heterocylesvia[3+2]cycloadditions to a vareity of multiple pi-bonds including C=C,C*C,C=O,C=S,C=N,N=N.

1.新型二外型亚甲基化合物和稠合异恶唑的合成我们制备并使用（三甲基甲硅烷基甲基）乙炔甲酸甲酯作为亲偶极试剂和共同关键化合物，产生二外型亚甲基化合物的前体，随后与烯烃以[4+2]环加成模式反应得到稠合杂环 化合物。我们发现了合成二外型亚甲基异恶唑啉前体的新通用路线，以及通过狄尔斯-阿尔德反应生成稠合异恶唑。2.通过路易斯介导的烯烃与3-甲硫基-4-三甲基甲硅烷基-1,2-丁二烯的[2+2]环加成反应获得二外型亚甲基环丁烷的新途径 在使用烯丙基硅烷和炔丙基硅烷进行有机合成的研究过程中，我们发现了一种合成二外型亚甲基环丁烷的新通用路线，即通过 3-甲硫基-4-三甲基甲硅烷基-1,2-丁二烯与路易斯酸促进的烯烃进行 [2+2] 环加成反应，然后依次反应生成砜 氧化和1,2-消除。二外型亚甲基环丁烷还成功地应用于通过与2-氧烯丙基阳离子的[4+3]环加成构建双环[5.2.0]壬烷环系统。标题化合物在形式上可被视为 1,2,3-丁三烯或 1,3-丁二烯-2,3-二基的合成等价物。3.羰基叶立德和相关 1,3-偶极试剂的生成和反应从合成和理论的角度来看，1,3-偶极试剂是重要且有趣的化学物质。我们发现，在温和和中性条件下，通过α-芳基取代的氯甲基三甲基硅基甲基醚的硅基1,3-消除确实可以方便地生成简单的羰基叶立德，否则无法获得，这提供了二氢呋喃和四氢呋喃及其相关化合物的强大一步合成。 杂环通过[3+2]环加成到多种多个π键上，包括C=C,C*C,C=O,C=S,C=N,N=N。

项目成果

Akira HOSOMI: "A New Access to Carbonyl Ylides by the Silicon-Based 1,3-Elimination and their [3+2]Cycloadditions to Alkencs and Alkynes: One-Step Synthesis of Dihydrofurans and Tetrahydrofurans" Tetrahedron Letters. 34. 5943-5946 (1993)

Akira HOSOMI：“通过硅基 1,3-消除及其 [3 2]环加成到烯和炔烃获得羰基叶立德的新途径：二氢呋喃和四氢呋喃的一步合成”四面体快报。

"Divergent Stereoselectivity in the Reduction of α,β-Epoxy Ketones Using Hydridosilicates" Tetrahedron Lett.35(印刷中). (1994)

“使用氢化硅酸盐还原 α,β-环氧酮时的不同立体选择性”Tetrahedron Lett.35（印刷中）。

T.Nishio, Y.Mori, and A.Hosomi: "Photochemical Reactions of Benzothiazole-2-thiones" J.Chem.Soc., Perkin Trans 1. (18). 2197-2200 (1993)

T.Nishio、Y.Mori 和 A.Hosomi：“苯并噻唑-2-硫酮的光化学反应”J.Chem.Soc.，Perkin Trans 1。(18)。

H.Aoyama, H.Sagae, and A.Hosomi: "A Novel Synthesis of 4-Spirocylopropyl beta-Lactams" Tetrahedron Lett.34 (37). 5951-5952 (1993)

H.Aoyama、H.Sagae 和 A.Hosomi：“4-螺环丙基 β-内酰胺的新颖合成”Tetrahedron Lett.34 (37)。

M.Hojo, H.Harada, C.Murakami, and A.Hosomi: "Direct Generation and Reactions of Sulfur-Substituted Allylcopper Reagents by a Novel Reduction Reaction Using Organocuprate" J.Chem.Soc., Chem.Commun.(in press.). (1994)

M.Hojo、H.Harada、C.Murakami 和 A.Hosomi：“通过使用有机铜的新型还原反应直接生成硫取代的烯丙基铜试剂”J.Chem.Soc.、Chem.Commun.（出版中）