Spontaneous Resolution, Asymmetric Catalysis, and Fluorescence Properties of Δ- and Λ-[Cu(Tzmp)]n Enantiomers from in Situ [2+3] Cycloaddition Synthesis
Spontaneous Resolution, Asymmetric Catalysis, and Fluorescence Properties of Δ- and Λ-[Cu(Tzmp)]n Enantiomers from in Situ [2+3] Cycloaddition Synthesis
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原位 [2 3] 环加成合成的 δ- 和 lambda-[cu(tzmp)]N 对映体的自发拆分、不对称催化和荧光特性。
DOI：
10.1021/acs.inorgchem.5b00478
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发表时间：
2015-06-01
影响因子：
4.6
通讯作者：
Wen, He-Rui
中科院分区：
文献类型：
--
作者：
Tang, Yun-Zhi;Xiong, Jian-Bo;Wen, He-Rui
虽然有一些心不在焉；或手性四唑配合物是通过Sharpless反应合成的，之前没有报道过通过原位[2+3]环加成合成自发拆分Cu(I)-四唑化合物。金属四唑化合物 [Cu(Tzmp)](n) (1) (HTzmp = 3-四唑甲基吡啶)的第一个对映体 Delta- 和 Lambda- 是通过柔性有机腈 (3-氰甲基吡啶) 与叠氮化钠在 CuCl2 作为路易斯酸存在下的原位 [2 + 3] 环加成反应获得和分离的。 Delta-1 和 Lambda-1 具有纯手性螺旋配位聚合物系统和 {4(4).6(2)} 二维框架。光致发光研究表明1在固态下表现出强烈的绿色荧光，最大发射峰在535 nm左右。值得注意的是，[Cu(Tzmp)](n) (1) 的 Delta- 和 Lambda- 催化对映选择性 Henry 反应，具有高产率（大于 96%）和一定的对映选择性（高达 69%）。
Although a number Of acentric; or chiral tetrazole complexes were synthesized from Sharpless reaction, there are no spontaneous resolution Cu(I)-tetrazole compounds from in situ [2 + 3] cycloaddition synthesis that have been reported before. The first enantiomers Delta- and Lambda- of metal tetrazole compound [Cu(Tzmp)](n) (1) (HTzmp = 3-tetrazolemethylpyridine) were obtained and isolated from in situ [2 + 3] cycloaddition reactions of a flexible organic nitrile (3-cyanomethylpyridine) with sodium azide in the presence of CuCl2 as the Lewis acid. Delta-1 and Lambda-1 feature a homochiral helical coordination polymeric system and {4(4).6(2)} two-dimensional framework. The photoluminescence Study suggests 1 exhibits strong green fluorescence in solid state With maximal emission peaks around 535 nm. Remarkably, the Delta- and Lambda- of [Cu(Tzmp)](n) (1) catalyzes the enantioselective Henry reaction with high yield (More than 96%) and certain enantioselectivity (up to 69%).