An unusual endo-selective C-H hydroarylationof norbornene by the Rh(I)-catalyzed reactionof benzamides.
An unusual endo-selective C-H hydroarylationof norbornene by the Rh(I)-catalyzed reactionof benzamides.
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DOI：
10.1038/s41467-017-01531-2
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发表时间：
2017-11-13
影响因子：
16.6
通讯作者：
Chatani N
中科院分区：
文献类型：
--
作者：
Shibata K;Natsui S;Tobisu M;Fukumoto Y;Chatani N
氢化芳基化是一种环境吸引力的策略，其将底物中所含的所有原子并入所需的产物中。几乎所有的氢化芳基化的藜芦烯报道日期涉及外选择性反应。在这里，我们展示了在Rh（I）催化的芳香酰胺的反应中的内选择性氢化芳基化。空间体积大的羧酸的加入增强了反应的内选择性。氘标记实验结果表明，在氢化芳基化产物中，芳香酰胺的邻位碳原子和邻位氢原子都连接在正戊烷骨架的同一个碳原子上。这些结果清楚地表明，加氢金属化或碳化，这是普遍接受的机制，催化加氢芳基化的C-H键，不涉及作为关键步骤在本反应中，并表明，该反应涉及铑卡宾络合物产生的作为关键中间体的异戊二烯。研究不寻常的有机金属途径可能有助于有效地控制均相催化中的产物选择性。在这里，作者报告了芳族酰胺与异戊烯衍生物的氢化芳基化反应，并提出了铑-卡宾中间体的形成，导致很少观察到的内产物。
Hydroarylation is an environmentally attractive strategy which incorporates all of the atoms contained in the substrates into the desired products. Almost all the hydroarylations of norbornene reported to date involve an exo-selective reaction. Here we show the endo-selective hydroarylation of norbornene in the Rh(I)-catalyzed reaction of aromatic amides. The addition of sterically bulky carboxylic acids enhances the endo-selectivity of the reaction. The results of deuterium-labeling experiments show that both the ortho-carbon and the ortho-hydrogen atoms of aromatic amides were attached to the same carbon atom of the norbornane skeleton in the hydroarylation product. These results clearly suggest that hydrometalation or carbometalation, which are commonly accepted mechanisms for the catalytic hydroarylation of C–H bonds, are not involved as the key step in the present reaction, and suggest that the reaction involves a rhodium carbene complex generated from norbornene as the key intermediate. Investigating unusual organometallic pathways may help to efficiently control product selectivity in homogeneous catalysis. Here, the authors report the hydroarylation of aromatic amides with norbornene derivatives and propose the formation of a rhodium-carbene intermediate leading to rarely observed endo-products.
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影响因子：
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