Ruthenium‐Catalyzed Propargylation of Aromatic Compounds with Propargylic Alcohols
Ruthenium‐Catalyzed Propargylation of Aromatic Compounds with Propargylic Alcohols
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DOI：
10.1002/ejoc.200500858
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发表时间：
2006-02
影响因子：
2.8
通讯作者：
Youichi Inada;M. Yoshikawa;M. Milton;Y. Nishibayashi;S. Uemura
中科院分区：
文献类型：
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作者：
Youichi Inada;M. Yoshikawa;M. Milton;Y. Nishibayashi;S. Uemura
具有末端炔基的丙炔醇与芳香族化合物在硫代酸桥接的二钌络合物的催化量下反应，得到相应的丙炔基化芳香族化合物，收率高，具有完全选择性。带有芳香基团的丙炔醇分子内反应顺利进行，产生高收率的环化产物，具有完全的选择性。钌-烯丙基配合物[Cp*RuCl(μ -2- sme)2RuCp*(=C=C=CHPh)]BF4 （Cp* = η -5- c5me5）与10个当量的2-甲基呋喃的化学计量反应以34%的产率生成2-甲基-5-（1-苯基-2-丙基）呋喃，表明这些催化反应是通过钌-烯丙基中间体进行的。该反应被认为是由钌稳定的丙炔阳离子取代芳香族化合物的亲电性反应。（©Wiley-VCH Verlag GmbH & Co. KGaA，德国Weinheim 69451, 2006）
Reactions of propargylic alcohols bearing a terminal alkyne moiety with aromatic compounds in the presence of a catalytic amount of thiolate-bridged diruthenium complexes give the corresponding propargylated aromatic compounds in high yields with complete selectivity. Intramolecular reactions of propargylic alcohols bearing an aromatic moiety proceed smoothly to afford the cyclized products in high yields with complete selectivity. The stoichiometric reaction of the ruthenium–allenylidene complex [Cp*RuCl(μ2-SMe)2RuCp*(=C=C=CHPh)]BF4 (Cp* = η5-C5Me5) with 10 equiv. 2-methylfuran results in the formation of 2-methyl-5-(1-phenyl-2-propynyl)furan in 34 % yield, indicating that these catalytic reactions proceed via ruthenium–allenylidene intermediates. The reaction is considered to be an electrophilic substitution of aromatic compounds by the ruthenium-stabilized propargyl cation. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)