Manganese-catalyzed synthesis of fluorinated organic compounds and hydrogenation/dehydrogenation catalysis

锰催化含氟有机化合物的合成及加氢/脱氢催化

• 批准号: 20K15305
• 负责人: HE YuTao
• 金额: $ 1.66万
• 依托单位: Okinawa Institute of Science and Technology Graduate University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Early-Career Scientists
• 财政年份: 2020
• 资助国家: 日本
• 起止时间: 2020-04-01 至 2021-03-31
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-20K15305/
• 关键词: manganese; coupling; oxidative addition

Until now, the following research achievements have been achieved.1. The synthesis of stable Mn(III) aryl complexes obtained by oxidative addition of aryl bromide or aryl chloridehas been finished.2. The reactions of our synthesized complexes with a range of organometallic alkylating or arylating reagents (alkyl and aryl Grignard reagents, MeLi, ZnMe2) to undergo C(sp2)-C(sp3) or C(sp2)-C(sp2) bond coupling has been carried out and a preliminary catalytic system has been demonstrated.3.The reagent scope and yield of the C(sp2)-C(sp3) coupled product can be increased by addition of TEMPO as an oxidant generating alkyl radicals.4.Except aryl bromide, the type of Ar-Cl is also a good pre-cursor in oxidative addition to MnI species for construc-tion of new C-C bond.

到目前为止，取得了以下研究成果：1.通过芳基溴化物或芳基氯化物的氧化加成，合成了稳定的Mn(III)芳基配合物。我们合成的化合物与一系列有机金属烷基化或芳基化试剂(烷基和芳基格氏试剂，Meli，ZnMe2)进行了C(Sp2)-C(Sp3)或C(Sp2)-C(Sp2)键的偶联反应，并初步建立了催化体系。3.加入TEMPO作为生成烷基自由基的氧化剂，可以扩大C(Sp2)-C(SP3)偶联产物的试剂范围和产率。4.除芳基溴外，除芳基溴外，Ar-Cl也是除MnI以外的良好的C-C键结构的氧化前催化剂。