TRANSITION-METAL-CATALYZED REACTIONS OF DIAZO-COMPOUNDS .2. ADDITION TO AROMATIC-MOLECULES - CATALYSIS OF BUCHNER SYNTHESIS OF CYCLOHEPTATRIENES
TRANSITION-METAL-CATALYZED REACTIONS OF DIAZO-COMPOUNDS .2. ADDITION TO AROMATIC-MOLECULES - CATALYSIS OF BUCHNER SYNTHESIS OF CYCLOHEPTATRIENES
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DOI：
10.1021/jo00318a010
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发表时间：
1981-01-01
影响因子：
3.6
通讯作者：
TEYSSIE, P
中科院分区：
文献类型：
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作者：
ANCIAUX, AJ;DEMONCEAU, A;TEYSSIE, P
在室温下，贫电子铑（II）羧酸盐[四（全氟羧酸）二铑（II）]可以有效地催化卡宾（由重氮酯产生）与芳香分子的加成。该反应以非常好的产率容易地得到1-烷氧羰基环庚-2，4，6-三烯（动力学非共轭异构体）。观察到的区域选择性合理化的攻击方面的高度亲电类卡宾物种的芳香族分子。催化剂的竞争性还原同时发生，并负责缓慢deactivationof的system.Since Buchner的经典工作，环庚三烯的化学已充分讨论的文献。然而，高效和选择性地合成取代环庚三烯的问题仍然没有解决。事实上，由于三烯体系的不稳定性，除了分子内反应，卡宾直接加成到芳族分子上会产生难以纯化的异构体混合物2（方案I）。我们对卡宾化学中过渡金属催化的一般性研究导致了羧酸铑（II）促进卡宾插入活性碳的高效发现，
The addition of carbenes (generated from diazo esters) to aromatic molecules is efficiently catalyzed at room temperature by electron-poor Rh (II) carboxylates [tetrakis (perfluorocarboxylato) dirhodium (II)]. The reaction gives ready access to l-carbalkoxycyclohepta-2, 4, 6-trienes (the kinetic nonconjugated isomer) in very good yield. The observed regioselectivities are rationalized in terms of an attack of a highly electrophilic carbenoid species on the aromatic molecule. A competitive reduction of the catalyst simultaneously occurs and is responsible for a slow deactivationof the system.Since Buchner’s classical work, the chemistry of cyclo-heptatrienes has been adequately discussed in the literature. However, the problem of efficient and selective synthesis of substituted cycloheptatrienes is still unsolved. Indeed, because of the lability of the triene system, except for intramolecular reactions, a direct addition of carbenes to aromatic molecules produces hard-to-purify mixtures of isomers2 (Scheme I). Our general investigations of transition-metal catalysis in carbene chemistry ledto the discovery of the high efficiency of rhodium (II) carboxylates for promoting the insertion of carbenes into activated