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:(1)研究了多种碳烯在区域选择性碳氢插入或烷氧化合物中的最佳反应条件。(2)除烷氧化合物外，还研究了其他被碳烯选择性插入的底物。烯醇酸阴离子、腈碳离子和烷基锂离子可选择性插入-碳氢键。1989:(3)发现了t-BuOK在低温下对溴代烷类化合物反应的促进作用，并对其作为碳源的反应性进行了研究。(4)环丙醇衍生物如环丙酮半缩醛和氰醇与无负载羰基反应，得到新型开环丙酸环加合物，收率高。(5)研究了一种新型的环乙基碳烯-亲核试剂的三组分联合反应，发现氧鎓化物中间体的生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。

Akira Oku: "Stereochemical Aspects in the Insertion by Alkylidenemethylene Carbenoids into the -C-H Bond of Alkoxides." J.Org.Chem.53. 3086-3098 (1988)

Akira Oku：“亚烷基亚甲基类胡萝卜素插入醇盐 -C-H 键中的立体化学方面。”

A.Oku: "Novel Ring-Opening Addition Reaction of Cyclopropanols with Carbenes" J.Chem.Soc.,Chem.Commun.1990. (1990)

A.Oku：“环丙醇与卡宾的新型开环加成反应”J.Chem.Soc.，Chem.Commun.1990。