一种手性锌氮配合物,即一种2(S)-{4S-异丙基-2-[2-(4S-异丙基-4,5-二氢化-2-噁唑啉基)-苯基]-4,5,-二氢化-1-咪唑啉基}-3-甲基-1-丁醇氯化锌配合物,其特征在于由1,2-二腈基苯和L-缬氨醇在无水无氧条件下和催化剂无水氯化锌制备的、由以下化学式所示的配合物:该配合物(I)的合成方法,由1,2-二腈基苯和L-缬氨醇在无水无氧条件下和催化剂无水ZnCl2(40-50mol%)于氯苯溶剂中回流反应24小时,然后分离、纯化,即反应结束后脱去氯苯,加水溶解后用氯仿萃取,萃取相脱溶后用柱层析纯化;配合物(I)用石油醚及二氯甲烷淋洗,柱层析分离,自然挥发得配合物单晶。该配合物在2-甲基苯甲醛的腈硅化反应中显示较好的催化性能,其转化率高达96%。
【技术实现步骤摘要】
本专利技术涉及一种金属有机配位化合物(配合物)及其制备方法,特别涉及含氮的手性金属有机配合物及其制备方法,确切地说是一种手性噁唑啉金属有机配合物及其合成方法。
技术介绍
随着有机化学的发展,金属有机化合物在有机合成中的应用愈来愈广,是现在有机化学中极为活跃的领域之一,已经广泛应用于有机合成反应中。20世纪60年代后期出现的使用手性配体与过渡金属络合物催化的不对称合成反应大大加速了手性药物的研究。化学催化不对称合成法的重要内容便是手性配体及含金属催化剂的设计1-9,从而使反应具有高效和高对映选择性。近年来手性锌噁唑啉、咪唑啉金属配合物在不对称催化领域取得了较好的催化效果。10-13参考文献1. Coordination properties of zinc 5, 15_di (o-aminopheny 1) octaalkylporphyrin in reactions with mono—and dibasic nitrogen bases. Zaitseva, S. V. ;Zdanovitch, S. A. ;Koifman, 0.I.Russian Journal of Inorganic Chemistry (2010),55(10),1574-1580.2.Three zinc(II)complexes constructed from aromatic dicarboxylate andl,4-bis ((2-(pyridin-2-yl)-lH-imidazol-l-yl)methy1)benzene :Syntheses, crystal structures and luminescent properties. Liu, Guang-Xiang ;Xu, Yu-Yong ; Wang, Yan ;Nishihara, Sadafumi ;Ren, Xiao-Ming. Inorganica Chimica Acta(2010), 363(14),3932-3938.3. Synthesis, structures, and properties of zinc (II) and cadmium(II) complexes withl,2,4,5-tetrakis(imidazol-l-ylmethyl) benzene and multicarboxylate ligands. Hua, Qin ;Zhao, Yue ;Xu, Guan-Cheng ;Chen, Man-Sheng ;Su, Zhi ;Cai,Kai ;Sun, Wei-Yin. Crystal Growth & DesignUOIO),10(6),2553-2562.4. Metal carboxylate-phosphonates containing flexible N-donor co-ligands. Wang, Peng-Fei ;Duan, Yan ;Cao, Deng-Ke ;Li, Yi-Zhi ;Zheng, Li-Min. Dalton Transactions(2010),39(19),4559—4565.5. Synthesis, crystal structure and properties of Zn (II) and Cd (II) complexes with2- (4-isopropyl-4-methyl-5-oxo-4,5-dihydro-lH-imidazol-2-yl) nicotinic acid ligand. Hu, Fei-Long ;Yin, Xian-Hong ;Mi, Yan ;Zhang, Shan-Shan ;Luo, Wei-Qiang ;Zhuang, Yue. Inorganic Chemistry Communications (2010), 13(1), 33-36.6. Biomimetic zinc (II) and cobalt (II) complexes with tri-tert-butoxysilanethiolate and imidazole 1i gands-Structural and spectroscopic studies. Dolega, Anna ;Pladzyk, Agnieszka ;Baranowska, Katarzyna ;Jezierska, Julia. Inorganica Chimica Acta(2009),362(14),5085-5096·7. Syntheses, Structures,and Fluorescent Properties of 2-(lH-Imidazol-2-yl)phenols and Their Neutral Zn(II)Complexes. Eseola,Abiodun Omokehinde ;Li,Wen ;Gao,Rong ;Zhang,Min ;Hao,Xiang ;Liang,Tongling ;Obi-Egbedi, Nelson Okpako ;Sun,Wen-Hua. Inorganic Chemistry(Washington, DC,United States) (2009),48(19) ,9133-9146.8.New preparation of tridentate bis-oxazoline carbazole ligand effective for enantioselective Nozaki-Hiyama reaction. Inoue,Masahiro ;Nakada, Masahisa.,Heterocycles(2007),72 133-138.9.Syntheses, Structures,and Luminescent Properties of Zinc (II) and Cadmium(II) Coordination Complexes Based on Different (Pyridyl) imidazole Derivatives and 1,4-Benzenedicarboxylate. Lan, Ya-Qian ;Li,Shun—Li ;Fu, Yao-Mei ; Du, Dong-Ying ;Zang,Hong-Ying ;Shao, Kui-Zhan ;Su, Zhong-Min ;Fu, Qiang. Crystal Growth & Design (2009),9(3),1353-1360.10. Highly enantioselective hetero Diels-Alder reactions of N-sulfinyl dienophiIes promoted by copper (II)-and zinc (II)-chiral bis(oxazoline) complexes. Bayer, Annette ;Gautun,Odd R.Tetrahedron :Asymmetry(2001),12(21), 2937-2939.11. Bis(o本文档来自技高网...
【技术保护点】
1.一种手性锌氮配合物,即一种2(S)-{4S-异丙基-2-[2-(4S-异丙基-4,5-二氢化-2-噁唑啉基)-苯基]-4,5,-二氢化-1-咪唑啉基}-3-甲基-1-丁醇氯化锌配合物,其特征在于由1,2-二腈基苯和L-缬氨醇在无水无氧条件下和催化剂无水氯化锌制备的、由以下化学式所示的配合物:
【技术特征摘要】
【专利技术属性】
技术研发人员:罗梅,
申请(专利权)人:罗梅,
类型:发明
国别省市:34
还没有人留言评论。发表了对其他浏览者有用的留言会获得科技券。