手性席夫碱-铜(Ⅱ)与-钒氧(Ⅱ)配合物的合成及其在不对称氧化反应中的应用  

Synthesis of Chiral Schiff-base-Cu(Ⅱ) and -VO(Ⅱ) Complexes and Their Application in Enantioselective Oxidative Coupling

作　　者：周超[1] 陆维敏[1] 夏云超[1] 

机构地区：[1]浙江大学催化研究所,杭州310028

出　　处：《应用化学》2005年第2期142-147,共6页Chinese Journal of Applied Chemistry

摘　　要：由5种氨基酸与β- 萘酚醛或水杨醛反应合成了氨基酸席夫碱,以此为配体进一步合成了手性席夫 碱 -Cu2+配合物;将D- 氨基葡萄糖与β- 萘酚醛或水杨醛反应,合成了氨基葡萄糖席夫碱,再进一步合成了手性 席夫碱- VO2+的配合物。用红外光谱、元素分析、热重及核磁共振谱测试技术对配体及配合物进行了表征,并 探索了以上述2组配合物对联萘酚(BINOL)不对称合成反应催化作用。结果表明,L -氨基酸萘酚醛- Cu(Ⅱ) 配合物作催化剂,可得到最高收率81.7%,e.e.值为28.4%;氨基葡萄糖 -β -萘酚醛席夫碱 -钒氧(Ⅱ)配合物作 催化剂时,得到的联萘酚的收率为87.5%,光学活性60.3%e.e.,配合物中心离子(原子)的配位结构对产物 的光学活性值有较大影响。Five amino-acid Schiff bases and their corresponding Cu(Ⅱ) complexes as well as D-glucosamine Schiff bases and their corresponding V(Ⅳ) complexes were synthesized and characterized by means of elemental analysis, infrared absorption spectra, 1H NMR and TG. The catalytic activities of the complexes in the enantioselective oxidative couplings of β-napthol to BINOL were studied. The best result of yield and e.e. value are 81.7% and 28.4% for the Cu catalyst and 87.5% and 60.3% for the V catalyst. Experimental results show that the optical activity of the product was affected greatly by the coordination structure of the center ions.

关 键 词：席夫碱-钒氧配合物 席夫碱-铜配合物 不对称氧化偶合 联萘酚 氨基酸 Β-萘酚 

分 类 号：O641[理学—物理化学]