Rhodium(I)-Catalyzed Direct Carboxylation of Arenes with CO2 via Chelation-Assisted C-H Bond Activation
Rhodium(I)-Catalyzed Direct Carboxylation of Arenes with CO2 via Chelation-Assisted C-H Bond Activation
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DOI：
10.1021/ja109097z
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发表时间：
2011-02-09
影响因子：
15
通讯作者：
Iwasawa, Nobuharu
中科院分区：
文献类型：
--
作者：
Mizuno, Hajime;Takaya, Jun;Iwasawa, Nobuharu
首次实现了铑催化的未活化芳基C-H键在常压二氧化碳气氛下的直接羧化反应。在铑催化剂和化学计量的甲基化试剂AlMe 2（OMe）存在下，不同取代和官能化的2-芳基吡啶和1-芳基吡唑进行羧化反应，以良好的产率得到羧化产物。该催化剂由甲基铑（I）物种作为关键中间体组成，其经历C-H活化以提供铑（III），然后还原消除甲烷以得到亲核芳基铑（I）。该方法显示了C-H键活化策略在二氧化碳固定领域的应用前景。
Rh-catalyzed direct carboxylation of unactivated aryl C-H bond under atmospheric pressure of carbon dioxide was realized via chelation-assisted C-H activation for the first time. Variously substituted and functionalized 2-arylpyridines and 1-arylpyrazoles underwent the carboxylation in the presence of the rhodium catalyst and a stoichiometric methylating reagent, AlMe2(OMe), to give carboxylated products in good yields. The catalysis is proposed to consist of methylrhodium(I) species as the key intermediate, which undergoes C-H activation to afford rhodium(III), followed by reductive elimination of methane to give nucleophilic arylrhodium(I). This approach demonstrates promising application of C-H bond activation strategy in the field of carbon dioxide fixation.