Novel Carbon-Carbon Bond Formation Utilizing Selective C-H Bond Insertion by Carbenes.

利用卡宾选择性 C-H 键插入形成新型碳-碳键。

• 批准号: 63470080
• 负责人: OKU Akira
• 金额: $ 3.26万
• 依托单位: Kyoto 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 1989
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-63470080/
• 关键词: carbene; carbenoid; C-H insertion; organic synthesis; cyclopropanol; electron transfer; oxonium ylide; シクロプロパノ-ル; 電子移動反応; オキソニウムイオン

1988: (1) Optimized reaction conditions for regioselective C-H insertion or alkoxides by a variety of carbenes were examined. (2) In addition to alkoxides, other substrates which undergo selective insertion by carbenes were investigated. Enolate anion, nitrile carbanion, and alkyllithium were found to undergo selective - C-H insertion.1989: (3) Promotion effect of t-BuOK on the reaction of bromolithiocarbenoids at low temperatures was found and their reactivity as carbene sources was investigated. (4) Reaction of cyclopropanol derivatives such as cyclopropanone hemiacetals and cyanohydrins with unencumbered carbenes yielded novel ring-opened cycloadduct propionates in high yields. (5) A novel-type of three-component joint reactions between cyclic etliercarbene - nucleophile was investigated to find that the formation of oxonium ylide intermediate is the key step of this reaction.

1988年：（1）检查了各种碳烯的区域选择性C-H插入或烷氧化物的优化反应条件。 （2）除了烷氧化物外，还研究了其他通过卡宾斯选择性插入的底物。发现酸离阴离子，硝酸碳纤维和树基锂具有选择性-C-H插入。1989：（3）发现T-buok对低温下溴硫代基苯二酚对bromolithioxaroid的反应的促进作用，并研究了其反应性，因为研究了它们的反应性，因为研究了碳烯的反应性。 （4）环丙醇衍生物（例如环丙酮半乙酸酯和氰基氢蛋白与无固定的卡宾斯）的反应产生了高产量的新型环载环丙酸酯。 （5）研究了环状eTliercarbene-亲核试剂之间三分之一的关节反应的新颖类型，以发现Ylide中间体的形成是该反应的关键步骤。

项目成果

T. Harada, T. Katsuhira, A. Oku: "Stereoselective Synthesis of gem-Disubstuted Cyclopropanes from gem-Dibromocyclopropanes." Tetrahedron Lett., 30, 6039-6040 (1989).

T. Harada、T. Katsuhira、A. Oku：“从宝石二溴环丙烷立体选择性合成宝石取代环丙烷。”

T.Harada: "Stereoselective Synthesis of gem-Disubstituted Cyclopropanes from gem-Dibromocyclopropanes." Tetrahedron Lett.29. 6039-6040 (1989)

T.Harada：“从宝石二溴环丙烷立体选择性合成宝石二取代环丙烷。”

A.Oku: "Rhodium(II)-Catalyzed Intramolecular Carbenoid Reaction.Novel Ring-Cleaving Rearrangement of(Tetrahy drofurylacetyl)diazomethane" J.Am.Chem.Soc.

A.Oku：“铑（II）催化的分子内类胡萝卜素反应。（四氢呋喃乙酰基）重氮甲烷的新型环裂重排”J.Am.Chem.Soc。

T.Harada: "Generation and Alkylation of Lithium 1-Halocyclopropyl Zincate." Tetrahedron Lett.29. 6035-6038 (1989)

T.Harada：“1-卤代环丙基锌酸锂的生成和烷基化”。

Toshiro Harada: "Generation and Alkyaltion Reaction of 1-Bromoalkenylzincate." Tetrahedron Lett.29. 3821-3824 (1988)

Toshiro Harada：“1-溴烯基锌酸盐的生成和烷基化反应”。