Ruthenium-catalyzed hydrohydroxyalkylation of acrylates with diols and α-hydroxycarbonyl compounds to form spiro- and α-methylene-γ-butyrolactones.
Ruthenium-catalyzed hydrohydroxyalkylation of acrylates with diols and α-hydroxycarbonyl compounds to form spiro- and α-methylene-γ-butyrolactones.
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DOI：
10.1021/ja410533y
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发表时间：
2013-11-13
影响因子：
15
通讯作者：
Krische MJ
中科院分区：
文献类型：
--
作者：
McInturff EL;Mowat J;Waldeck AR;Krische MJ
在钌(0)催化的氢化烷基化条件下，邻二醇1a-1l和丙烯酸甲酯2a以优异的收率转化为相应的内酯3a-3l。丙烯酸甲酯2a与对苯甲酸甲酯1f、对苯甲酸二脱氢1f和对苯甲酸四脱氢1f反应生成相同的内酯3f，表明该过程可能以不依赖氧化还原水平的方式进行。多种取代丙烯酸酯2a-2h参与螺旋内酯的形成，如n -苄基-3-羟基氧吲哚10转化为环加合物4a-4h所示。羟基取代甲基丙烯酸酯2i与二醇1b、1f、1j和1l羟基烷基化反应生成α-外显亚甲基-γ-丁内酯5b、5f、5j和5l，收率中高。一个催化循环涉及1,2-二羰基-丙烯酸酯氧化偶联，形成恶环无环中间体的假设。用单晶x射线衍射对催化活性的单核钌配合物进行了表征。利用对取代1-苯基-1,2-丙二醇1g、1m和1n，通过密度泛函理论（DFT）计算，探讨了电子效应对非对称二醇反应区域选择性的影响。
Under the conditions of ruthenium(0) catalyzed hydrohydroxyalkylation, vicinal diols 1a–1l and methyl acrylate 2a are converted to the corresponding lactones 3a–3l in good to excellent yield. The reaction of methyl acrylate 2a with hydrobenzoin 1f, benzoin didehydro-1f, and benzil tetradehydro-1f form the same lactone 3f product, demonstrating that this process may be deployed in a redox level-independent manner. A variety of substituted acrylic esters 2a–2h participate in spirolactone formation, as illustrated in the conversion of N-benzyl-3-hydroxyoxindole 1o to cycloadducts 4a–4h. Hydrohydroxyalkylation of hydroxyl-substituted methacrylate 2i with diols 1b, 1f, 1j and 1l forms α-exo-methylene-γ-butyrolactones 5b, 5f, 5j and 5l in moderate to good yield. A catalytic cycle involving 1,2-dicarbonyl-acrylate oxidative coupling to form oxaruthenacyclic intermediates is postulated. A catalytically competent mononuclear ruthenium(II) complex was characterized by single crystal X-ray diffraction. The influence of electronic effects on regioselectivity in reactions of nonsymmetric diols were probed using para-substituted 1-phenyl-1,2-propanediols 1g, 1m and 1n and density functional theory (DFT) calculations.
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影响因子：
2.1
作者：
Eipert, M;Maichle-Mössmer, C;Maier, ME
通讯作者：
Maier, ME
影响因子：
3.6
作者：
Dhondi, Pawan K.;Carberry, Patrick;Chishohm, John D.
通讯作者：
Chishohm, John D.
影响因子：
15
作者：
Leung, Joyce C.;Geary, Laina M.;Chen, Te-Yu;Zbieg, Jason R.;Krische, Michael J.
通讯作者：
Krische, Michael J.
影响因子：
--
作者：
Bower, John F.;Krische, Michael J.
通讯作者：
Krische, Michael J.
影响因子：
16.6
作者：
Burstein, C;Glorius, F
通讯作者：
Glorius, F