Activation of Carbon-Carbon Bonds by Transition Metals

过渡金属对碳-碳键的活化

• 批准号: 19205013
• 负责人: MURAKAMI Masahiro
• 金额: $ 32.12万
• 依托单位: Kyoto University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 2007
• 资助国家: 日本
• 起止时间: 2007 至 2009
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-19205013/
• 关键词: 炭素-炭素結合切断; 炭素-炭素結合形成; 遷移金属触媒; 白金; 多環芳香族炭化水素; アズレン; 不活性結合活性化; 環化異性化反応; ロジウム; シクロブタノール; インダノール; 骨格転位; シクロブタノン; ニッケル

New carbon-carbon bond cleaving reactions catalyzed by transition metals were developed. Various carbon skeletons were constructed by utilization of these reactions. In particular, enantioselective cleavage of a carbon-carbon bond led to the formation of quaternary chiral carbon centers. For example, six-membered benzolactones having a chiral quaternary center at the benzylic position were synthesized with high enantioselectivity. Indane skeletones having chiral quaternary centers at both benzylic positions were constructed in a stereoselective manner from cyclobutanols with an aryl substituent at the 3-position. A new method to synthesize azulene derivatives, which were attractive as organic materials, was also developed.

发展了过渡金属催化的新的碳-碳键断裂反应。利用这些反应构建了各种碳骨架。特别是，碳-碳键的对映选择性断裂导致了季手性碳中心的形成。例如，具有较高对映体选择性的六元苯并内酮类化合物的合成具有很高的对映选择性。以3位芳基取代的环丁醇为原料，以立体选择性的方式合成了在两个苄基上都具有手性四元中心的吲哚骨架。还开发了一种新的方法来合成作为有机材料的蔚蓝衍生物。

项目成果

Rhodium-Catalyzed Asymmetric Synthesis of 3,4-Dihydrocoumarins via Enantioselective C-C Bond Cleavage of Cyclobutanones

铑催化环丁酮对映选择性 C-C 键断裂合成 3,4-二氢香豆素

• 发表时间: 2009
• 作者: Masahiro Murakami;Masanori Shigeno;Takanori Matsuda
• 通讯作者: Takanori Matsuda

ロジウム触媒による3-アリールシクロブタノールから1-インダノールへのエナンチオ選択的異性化反応

铑催化3-芳基环丁醇对映选择性异构化反应生成1-茚满醇

• 发表时间: 2009
• 作者: 山本泰河;重野真徳;村上正浩
• 通讯作者: 村上正浩

enantioselective synthesis of 1-indanols by rhodium-catalyzed activation of a carbon-carbon bond

铑催化碳-碳键活化对映选择性合成 1-茚满醇

• 发表时间: 2009
• 作者: 重野真徳;山本泰河;村上正浩
• 通讯作者: 村上正浩

Synthesis of 1(2H)-isoquinolones by the nickel-catalyzed denitrogenative alkyne insertion of 1,2,3-benzotriazin-4(3H)-ones

• DOI: 10.1021/ol8010826
• 发表时间: 2008-07-17
• 期刊: ORGANIC LETTERS
• 影响因子: 5.2
• 作者: Miura, Tomoya;Yamauchi, Motoshi;Murakami, Masahiro
• 通讯作者: Murakami, Masahiro

Palladium-catalyzed sequential carbon-carbon bond cleavage/formation producing arylated benzolactones.

• DOI: 10.1021/ol802218a
• 发表时间: 2008-10
• 期刊: Organic letters
• 影响因子: 5.2
• 作者: T. Matsuda;Masanori Shigeno;M. Murakami