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碳-碳键断裂反应。利用这些反应构建了各种碳骨架。特别地，碳-碳键的对映选择性裂解导致季手性碳中心的形成。例如，在苄基位置具有手性季中心的六元苯并内酯以高对映选择性合成。以立体选择性的方式，从3-位带有芳基取代基的环丁醇出发，合成了在两个苄基位置都具有手性季中心的吲哚酮。同时，还发展了一种新的合成方法，合成了一类具有广泛应用前景的有机材料--甘菊环衍生物。

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

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

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

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