Conversion of Allylic Alcohols to Carbonyl Compounds Catalyzed by Alkoxy-Bridged Dinuclear Areneruthenium Complexes
Conversion of Allylic Alcohols to Carbonyl Compounds Catalyzed by Alkoxy-Bridged Dinuclear Areneruthenium Complexes
复制标题
DOI：
10.1021/om050442p
复制
发表时间：
2005-09
期刊：
影响因子：
2.8
通讯作者：
Yasutomo Takai;R. Kitaura;Emi Nakatani;Takafumi Onishi;H. Kurosawa
中科院分区：
文献类型：
--
作者：
Yasutomo Takai;R. Kitaura;Emi Nakatani;Takafumi Onishi;H. Kurosawa
在可见光照射下，[Ru2(η6：η1：η1：μ-C6H5(CH2)3 O}2(μ-C6H5N=NC6H4OMe)]BF4连接的偶氮苯桥联双核Ru配合物在温和的条件下能够催化烯丙醇异构化为相应的羰基化合物.氯桥双核配合物[Ru2{η6：η1：μ-C6H5(CH2)3 O}2-(μ-Cl)]BF4与1当量AgOTf或甲氧基桥联配合物[Ru2[η6：η1：μ-C6H5-(CH2)3 O}2(μ-OME)]BF4与HOTf反应也产生了异构化催化剂，而这些双核配合物本身作为异构化催化剂是无效的.氢化物桥联双核配合物[Ru2{η6：η1：μ-C6H5(CH2)3 O}2(μ-H)]BF4与甲基乙烯基酮反应生成烯丙氧基桥联双核配合物[Ru2{η6：η1：μ-C6H5(CH2)3O}2-(μ-OCHMeCH=CH2)]BF4，而相同的反应物在等摩尔量的HOTf存在下，迅速生成CH3 COCH2 CH3和三氟络合物[Ru2{η6：η1：μ-C6H5(CH2)3 O}2(μ-OTf)]BF4。讨论了以双核受体[Ru2{η6：η1：μ-C6H5(CH2)3 O}2]2+为关键物种的烯丙醇异构化反应的机理.
Visible light irradiation of an azobenzene-bridged dinuclear ruthenium complex ligated by a η 6 -arene group having a pendant alkoxy ligand, [Ru 2 {η 6 :η 1 :μ-C 6 H 5 (CH 2 ) 3 O} 2 (μ-C 6 H 5 N=NC 6 H 4 OMe)]BF 4 , led to generation of an active species capable of catalyzing isomerization of allyl alcohols to the corresponding carbonyl compounds under mild conditions. Treatment of the chloro-bridged dinuclear complex [Ru 2 {η 6 :η 1 :μ-C 6 H 5 (CH 2 ) 3 O} 2 -(μ-Cl)]BF 4 with 1 equiv AgOTf or that of the methoxy-bridged complex [Ru 2 {η 6 :η 1 :μ-C 6 H 5 -(CH 2 ) 3 O} 2 (μ-OMe)]BF 4 with HOTf also resulted in generation of catalyst for the isomerization, while these dinuclear complexes themselves were inactive as the isomerization catalyst. Reaction of the hydride-bridged dinuclear complex [Ru 2 {η 6 :η 1 :μ-C 6 H 5 (CH 2 ) 3 O} 2 (μ-H)]BF 4 with methyl vinyl ketone gave the allyloxy-bridged dinuclear complex [Ru 2 {η 6 :η 1 :μ-C 6 H 5 (CH 2 ) 3 O} 2 -(μ-OCHMeCH=CH 2 )]BF 4 rather sluggishly, while the same reactants in the presence of an equimolar amount of HOTf rapidly gave CH 3 COCH 2 CH 3 and the triflate complex [Ru 2 {η 6 : η 1 :μ-C 6 H 5 (CH 2 ) 3 O} 2 (μ-OTf)]BF 4 . A mechanistic scheme for the isomerization of allyl alcohols involving the dinuclear acceptor [Ru 2 {η 6 :η 1 :μ-C 6 H 5 (CH 2 ) 3 O} 2 ] 2 + as a key species has been discussed.