Ortho-selective allylation of 2-pyridylarenes with allyl acetates catalyzed by ruthenium complexes
Ortho-selective allylation of 2-pyridylarenes with allyl acetates catalyzed by ruthenium complexes
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DOI：
10.1021/om060561k
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发表时间：
2006-09-25
期刊：
影响因子：
2.8
通讯作者：
Inoue, Yoshio
中科院分区：
文献类型：
--
作者：
Oi, Shuichi;Tanaka, Yoshikazu;Inoue, Yoshio
在Ru(II)-膦络合物存在下，2-吡啶并芳烃的邻位与乙酸烯丙基酯选择性地烯丙化。在芳香取代的乙酸烯丙酯的情况下，如乙酸肉桂酯，线性烯丙化化合物是主要的产物。然而，与直链脂肪族乙酸烯丙酯的反应得到线形和支化产物的混合物，而与支链脂肪族烯丙基乙酸酯的反应优先提供线形产物。根据这些结果，提出了反应机理是通过2-吡啶基配位到Ru中心的Sigma-烯丙基Ru中间体的配位，生成了Sigma-烯丙基和Pi-CallylRu中间体，并通过Sigma-CallylRu中间体邻位生成了2-吡啶并芳烃。
The ortho-position of 2-pyridylarenes is selectively allylated with allyl acetates in the presence of a ruthenium(II)-phosphine complex. In the case of aromatic-substituted allyl acetates, such as cinnamyl acetate, linear allylated compounds were the predominant products. However, the reaction with linear aliphatic allyl acetates afforded a mixture of linear and branched products, whereas reactions with branched aliphatic allyl acetates afforded linear products preferentially. From these results, the reaction mechanism is proposed to involve the formation of sigma-allyl- and pi-allylruthenium intermediates and ortho-ruthenation of the 2-pyridylarenes via the sigma-allylruthenium intermediate directed by coordination of the 2-pyridyl group to the ruthenium center.