Redox-neutral rhodium-catalyzed C-H functionalization of arylamine N-oxides with diazo compounds: primary C(sp(3))-H/C(sp(2))-H activation and oxygen-atom transfer.
Redox-neutral rhodium-catalyzed C-H functionalization of arylamine N-oxides with diazo compounds: primary C(sp(3))-H/C(sp(2))-H activation and oxygen-atom transfer.
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DOI：
10.1002/anie.201505302
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发表时间：
2015-10
影响因子：
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通讯作者：
Bing Zhou;Zhaoqiang Chen;Ya-xi Yang;Wen Ai;Huanyu Tang;Yunxiang Wu;Weiliang Zhu;Yuanchao Li
中科院分区：
文献类型：
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作者：
Bing Zhou;Zhaoqiang Chen;Ya-xi Yang;Wen Ai;Huanyu Tang;Yunxiang Wu;Weiliang Zhu;Yuanchao Li
在铑（III）催化下，1-萘胺N-氧化物与重氮化合物发生区域选择性氧化还原中性成环反应，合成了多种具有生物活性的1H-苯并[g]吲哚。该偶联反应在温和的反应条件下进行，并且不需要外部氧化剂。唯一的副产品是氮和水。更重要的是，该反应代表了未活化的伯C（sp（3））NH键和C（sp（2））NH键与重氮羰基化合物的双重官能化的第一个实例。DFT计算表明，中间体亚胺最有可能参与催化循环。此外，铑（III）催化的偶联容易获得的叔苯胺N-氧化物与α-重氮丙二酸酯也开发在外部无氧化剂的条件下，通过O-原子转移反应，以获得各种氨基扁桃酸衍生物。
An unprecedented rhodium(III)-catalyzed regioselective redox-neutral annulation reaction of 1-naphthylamine N-oxides with diazo compounds was developed to afford various biologically important 1H-benzo[g]indolines. This coupling reaction proceeds under mild reaction conditions and does not require external oxidants. The only by-products are dinitrogen and water. More significantly, this reaction represents the first example of dual functiaonalization of unactivated a primary C(sp(3) )H bond and C(sp(2) )H bond with diazocarbonyl compounds. DFT calculations revealed that an intermediate iminium is most likely involved in the catalytic cycle. Moreover, a rhodium(III)-catalyzed coupling of readily available tertiary aniline N-oxides with α-diazomalonates was also developed under external oxidant-free conditions to access various aminomandelic acid derivatives by an O-atom-transfer reaction.