新型手性膦噁唑啉铱络合物的合成及其在氢化反应中的应用  

Synthesis of Novel Chiral Ir-Phosphine-Oxazoline Complexes and Their Application in Asymmetric Hydrogenation of Olefins

作　　者：孟祥燕 梁建英 沈剑锋 樊伟明 MENG Xiang-yan LIANG Jian-ying SHEN Jian-feng FAN Wei-ming(Zhejiang Zhenyuan Pharmaceutical Co., Ltd., Shaoxing 312071, China)

机构地区：[1]浙江震元制药有限公司,浙江绍兴312071

出　　处：《合成化学》2016年第10期866-869,874,共5页Chinese Journal of Synthetic Chemistry

基　　金：浙江省自然科学基金资助项目(Y405013)

摘　　要：在鹰爪碱诱导下,2-氯甲基-4,4-二甲基噁唑啉与叔丁基苯基膦硼烷经络合反应,以43%的收率合成了光学纯度大于99%,手性中心在P上的新型手性噁唑啉氮膦配体(3);3和铱配合物([Ir(cod)Cl]2)经络合反应以55%的收率制得两个新型手性膦噁唑啉铱络合物催化剂(1和2),其结构经1H NMR,13C NMR,31P NMR和元素分析表征。考察了1和2对烯烃的不对称氢化反应的催化性能。结果表明:1具有较好的催化能力,收率>92%,但催化剂的手性诱导能力较差(ee≤36%)。A novel chiral oxazoline-phosphine ligand（3） with 99% ee in 43% yield was prepared by reaction of tert-butylphenylphosphine-borane with 2-（ chloromethyl ） -4,4-dimethyl-4,5-dihydrooxazole in the present of （ - ）-sparteine. Two novel chiral Ir-phosphine-oxazoline complexes （1 and 2） with chiral center in phosphine atom were synthesized by complexation reaction of 3 with [ Ir（cod） C1 ] 2. The structures were characterized by tH NMR, 13C NMR, 31p NMR and elemental analysis. The catalytic performance of 1 and 2 in the hydrogenation of olefins were investigated. The results showed that 1 exhibited good catalytic activity with 〉92% yield and modest enantioselectivities（ 〈 36% ）.

关 键 词：2-氯甲基-4 4-二甲基噁唑啉 叔丁基苯基膦硼烷 噁唑啉氮膦配体 铱络合物 合成 不对称氢化 催化 

分 类 号：O621.3[理学—有机化学] O614.82[理学—化学]