Development of New Reactive Intermediates on the Basis of the Reactions of Functionalized Highly Strained Molecules

基于功能化高应变分子反应开发新型反应中间体

• 批准号: 63470013
• 负责人: NAKAMURA Eiichi
• 金额: $ 4.61万
• 依托单位: Tokyo Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1988
• 资助国家: 日本
• 起止时间: 1988 至 1990
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-63470013/
• 关键词: Cycloaddition; Tetrahydrofuran; Dicarbonyl compounds; Cyclopropene; Asymmetric synthesis; Five-membered rings; テトラヒドロフラン; シクロプロパノン; シクロプロペノン; 歪み化合物; ラクトン; 超高圧反応; シクロペンタン; トリメチレンメタン

Aim of the Research : This program is directed toward the development of new reactive intermediates and new reactions by taking advantage of the internal chemical energy stored in strained molecules.Results : The following three reactions have been developed. (1) New thermal [3+2] cycloaddition. The reaction of 2, 2-dialkoxy-1-methylenecyclopropane with electron-deficient olefins under mild thermal conditions gives cyclopentanes in high yield. A similar reaction with carbonyl compounds affords substituted tetrahydrofurans. The mechanism and the nature of the reactive intermediate have been elucidated by kinetic and theoretical studies. (2) Carbometalation reaction. Addition of organometallics to cyclopropenone acetals provided a new entry to the chemistry of cyclopropyl metal compounds, which was further applied to the asymmetric synthesis of optically active compounds. (3) Synthesis of dicarbonyl compounds. Palladium-catalyzed reaction of cyclopropanone acetals with aryl triflates in the presence of carbon monoxide provided a new entry to the synthesis of 1, 4-dicarbonyl compounds.

研究的目的：该程序是针对新的反应性中间体和新反应的开发，它利用了骨折分子中存储的内部化学能。分析：已经发展了以下三个反应。 （1）新的热[3+2]环加成。在温和的热条件下，2，2-二甲基-1-甲基丙烷与电子缺陷烯烃的反应可使环戊烷高产量。与羰基化合物的类似反应可取代四氢呋喃。动力学和理论研究已经阐明了反应性中间体的机制和性质。 （2）碳测量反应。在环丙酮乙烯乙烯剂中添加有机金属为环丙基金属化合物的化学物质提供了新的入口，该化学进一步应用于光学活性化合物的不对称合成。 （3）双骨化合物的合成。在一氧化碳存在下，环丙酮乙酰酮与芳基三酯的反应为合成1，4-二甲苯化合物的新入口提供了新的入口。

项目成果

S.Yamago: "Use of Methylenecyclopropanone Ketals for Cyclopentane Synthesis.A New Efficient Thermal【3+2】Cycloaddition" J.Am.Chem.Soc.111. 7285-7286 (1989)

S.Yamago：“使用亚甲基环丙酮缩酮合成环戊烷。一种新的高效热法【3+2】环加成”J.Am.Chem.Soc.111（1989）。

S.Yamago,E.Nakamura: "Thermal〔3+2〕Heterocycloaddition Approach to Functionalized Tetrahydrofurans" J.American Chemical Society.

S. Yamago、E. Nakamura：“官能化四氢呋喃的热 [3+2] 杂环加成方法”J. 美国化学会。

S.Aoki: "synthesis of 1,4ーDicarbonyl Compounds by palladiumーCatayzed Cabonylative Arylation of Siloxycycloproanes" Syn bett. 741-742 (1990)

S.Aoki：“通过钯催化甲硅烷氧基环丙烷的羰基化芳基化合成 1,4-二羰基化合物”Syn bett 741-742 (1990)。

T.Fujimura: "Synthesis of 1.4ーKeto Estesrs,and 1,4ーDiketones via PalladiumーCatalyzed Acylation of Siloxycyclpropanes.Synthetic and Mechanisties" J.ovg.Chem. (1991)

T.Fujimura：“通过钯催化的甲硅烷氧基环丙烷酰化合成 1.4-酮酯和 1,4-二酮。合成和机理”J.ovg.Chem。

M.Isaka: "Applications of Metalated Cyclopropenone Ketals in a General Synthesis of Cyclopropenones.An Efficient Synthesis of the Antibiotic penitricir" J.Org.Chem. 54. 4727-4729 (1989)

M.Isaka：“金属化环丙烯酮缩酮在环丙烯酮通用合成中的应用。抗生素青霉素的有效合成”J.Org.Chem。