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新型四齿手性含硫(氮)配体的合成及其在芳香酮不对称氢转移中的应用

Synthesis of Novel Tetradentate Chiral Sulphur( nitrogen)-containing Ligands and Their Application in Asymmetric Transfer Hydrogenation
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摘要 以(1R,2R)-环己二胺酒石酸盐为原料,分别与2-噻唑甲醛和4-咪唑甲醛经缩合反应合成了两个四齿手性亚胺配体——(1R,2R)-N,N'-二(2-噻唑基)-1,2-环己二胺(L1,CCDC:1 003 830)和(1R,2R)-N,N'-二(4-咪唑基)-1,2-环己二胺(L2),其中L1为新化合物,其结构经1H NMR,ESI-MS,元素分析和X-单晶衍射表征。研究了L1和L2分别与金属络合物[MR]经原位反应制得的催化剂(Cat1M和Cat2M)对苯乙酮经不对称氢转移反应合成手性α-苯乙醇的催化性能。结果表明:L1与[Ir Cl(cod)]2经原位反应制得的催化剂Cat1Ir的催化活性优于Cat2Ir。以异丙醇为氢源,在异丙醇/氢氧化钾反应体系中,研究了Cat1Ir对芳香酮的不对称氢转移。结果表明:Cat1Ir能有效地催化还原芳香酮,大部分芳香酮的转化率均>99%。 Two chiral sulphur （nitrogen） -containing tetradentate ligand, （ 1R, 2R） -N, N＇-bis （ 2-thia- zolyl） -1,2-cyclohexyldiimine （ L1 ） and （ 1R, 2R ） -N, N＇-bis （ 4-imidazolyl ） -1,2-cyclohexyldiimine （L2）, were synthesized by condensation of 1,2-cyclohexyldiimine with 2-thiazole and 4-imidazole, respectively. L1 （CCDC： 1 003 830） was a novel compound and the structure was characterized by 1H NMR, ESI-MS, elemental analysis and X-ray single crystal diffraction. Two series of catalysts, CatI and Cat2, were prepared by reaction in-suit of L1 or I2 with metal complexes[ MR]. The catalytic activities of Cat1 and Cat2 were investigated by asymmetric transfer hydrogenation （ATH） of acetophenone with i-PrOH. The results showed that Cat3Ir, which was obtained by reaction in-suit of Cat1 with [ IrCl （cod） ] 2, exhibited better catalytic activity than Cat2Ir. Catalytic activities of 1 Catlr were investigated by ATH of aromatic ketones in i-PrOH/KOH. The results indicated that aromatic ketones with conversion of 〉 99% were reduced to chiral secondary aromatic alcohol, using Cater as the catalyst.
作者 于会娟 赵营 何军 莫伟杰 余林
机构地区 广东工业大学轻工化工学院
出处 《合成化学》 CAS CSCD 2015年第7期569-573,共5页 Chinese Journal of Synthetic Chemistry
基金 国家自然科学基金资助项目(21306026) 2014广东工业大学创新创业项目
关键词 手性四齿配体 不对称氢转移 芳香酮 手性芳香醇仲醇 合成 催化活性 tetradentate chiral ligand asymmetric transfer hydrogenation aromatic ketone chiralsecondary aromatic alcohol synthesis catalytic activity
分类号 O626 [理学—有机化学] O643.36 [理学—物理化学]
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参考文献12

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共引文献1

合成化学
2015年 第7期

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