吡啶基桥联双四唑钌(II)配合物催化酮的转移氢化反应

doi:10.1016/S1872-2067(17)62994-2

摘要/Abstract

摘要：

含氮配体具有稳定性好、易于合成等优点，而且其过渡金属配合物表现出较高的催化活性，因而在配位化学和均相催化等研究领域受到了广泛关注.基于吡啶骨架的三齿NNN配体具有良好的配位能力和丰富的配位模式，如吡啶桥联的对称配体2，2'：6'，2"-三吡啶、2，6-双噁唑啉基吡啶、2，6-双亚胺基吡啶和2，6-双吡唑基吡啶等在有机合成及配合物催化剂制备等方面得到广泛应用.2，6-双四唑基吡啶也是基于吡啶的多齿配体，已被用于合成发光材料或高效回收次锕系元素等，但是其在催化领域的应用较少.
过渡金属催化的不饱和化合物的转移氢化反应具有反应条件温和、不直接使用氢气等优点，因而受到越来越多的关注.一系列优异的配体及配合物在转移氢化反应中脱颖而出，如对甲苯磺酰手性二胺配体、2-甲胺基吡啶钌配合物、配体中含有NH官能团的过渡金属配合物等.我们也报道了几种吡啶基桥联的含氮配体及其钌配合物，并应用于催化酮的转移氢化反应.在此基础上，本文合成了三种连有不同膦配体的2，6-双四唑基吡啶钌配合物，并用于催化酮的转移氢化反应.
从N²，N⁶-二对甲苯基-2，6-吡啶二甲酰胺（1）出发，经氯代/环化两步反应合成4-氯吡啶基桥联双四唑化合物（2），配体2与RuCl₂（PPh₃）₃在对应的反应条件下制得三种连有不同膦配体的2，6-双四唑基吡啶钌配合物（3），其分子结构通过核磁共振波谱和X射线单晶晶体结构测定得到确认.将这三种钌配合物应用于催化酮的转移氢化反应，当催化剂用量为0.5 mol%时，在异丙醇回流条件下，比较连有不同膦配体的2，6-双四唑基吡啶钌配合物的催化活性.膦配体为1，4-双（二苯基膦）丁烷的钌配合物3b表现出更高的催化活性，含有双三苯基膦的钌配合物3a则表现出与3b相当或略低的催化活性，含有1，5-双（二苯基膦）戊烷的钌配合物3c活性最差.以3b为催化剂拓展了一系列酮底物，取代的芳香酮、链状和环状的脂肪酮都可以高效地被还原，大部分酮底物以>95%的转化率还原成相应的醇.含有氯取代基的苯乙酮对反应有较大的加速作用，反应时间更短，转化率更高.由于羰基环的张力，1-四氢萘酮与9-芴酮转化率略低.
结合实验结果与相关文献，提出了一条基于Ru-H活性中间体的内层反应机理：钌配合物在iPrOK作用下生成Ru（Ⅱ）-烷氧基中间体I，随后发生β-H消除反应脱去一分子丙酮得到Ru-H配合物，Ru-H配合物与酮底物作用经过渡态Ⅱ生成另一分子Ru（Ⅱ）-烷氧基中间体Ⅲ，随后异丙醇与烷氧基发生交换生成目标产物，同时生成中间体I完成催化循环.

关键词: 2,6-双四唑基吡啶, 钌, 转移氢化, 酮, 均相催化

Abstract:

Three ruthenium(Ⅱ) complex catalysts bearing 2,6-bis(tetrazolyl)pyridine were synthesized, structurally characterized, and applied in the transfer hydrogenation of ketones. Their different catalytic activities were attributed to the different phosphine ligands on the 4-chloro-2,6-bis(1-(p-tolyl)-1H-tetrazol-5-yl)pyridine ruthenium(Ⅱ) complexes, with that based on 1,4-bis(diphenylphosphino) butane exhibiting better catalytic activity. A variety of ketones were reduced to their corresponding alcohols with >95% conversion.

Key words: 2,6-Bis(tetrazolyl)pyridine, Ruthenium, Transfer hydrogenation, Ketone, Homogeneous catalysis

王连弟, 刘婷婷. 吡啶基桥联双四唑钌(II)配合物催化酮的转移氢化反应[J]. 催化学报, 2018, 39(2): 327-333.

Liandi Wang, Tingting Liu. Ruthenium(Ⅱ) complex catalysts bearing a 2,6-bis(tetrazolyl)pyridine ligand for the transfer hydrogenation of ketones[J]. Chinese Journal of Catalysis, 2018, 39(2): 327-333.

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