新型卡宾配体的合成及其在烯丙基烷基化催化反应中的应用  

The synthesis of carbene ligands and the application for allylic alkylation reaction

作　　者：张成路[1] 赵宝成[1] 孙鹏[1] 曲瑞峰[1] 朱长安[1] 王雪[1] 柴金华[1] 

机构地区：[1]辽宁师范大学化学化工学院生物技术与分子药物研发辽宁省重点实验室,辽宁大连116029

出　　处：《辽宁师范大学学报（自然科学版）》2013年第2期224-228,共5页Journal of Liaoning Normal University:Natural Science Edition

基　　金：辽宁省高校创新团队项目(2008T2017);辽宁省教育厅科学技术研究项目(2009A426)

摘　　要：以L-苯丙氨醇为起始原料,经过氨基的氯乙酰基化、与苯并咪唑偶联和噁唑啉构筑等3步反应成功实现了中间体4的合成,总收率达到56.3%,并首次确定了中间体4的绝对构型.最后以乙腈为溶剂,用6种卤代芳烃在不同反应条件下较高产率地合成了5个具有单噁唑啉环和1个具有双噁唑啉环的新型目标配体(5a-5f),最高收率为87.7%,其中双噁唑啉环配体结构具有1个C2轴,此结构是当今此类配体研究的热点.同时,应用所设计的配体催化烯丙基烷基化反应,在最优配体和最优条件下,以1,3-二苯基-2-烯丙基乙酸酯作为底物的反应,配体5a使得反应收到了较好的催化效果,最优收率为73.5%.A new class of benzimidazole carbine ligands containing oxazoline have been synthesized u- sing L-phenylalaninol as starting materials. In the synthesis,the protection of amino group,the cross- coupling with benzimidazole and the construction of oxazoline were operated. The key intermediate 4 was successfully achieved,in which the yields were 56.3 %. It is the first time to identify the absolute structure of 4. Six new target ligands were successfully synthesized in high yield and the different ar- yl halogenation were used in different temperature conditions. The highest yield reached 87.7%. In the six ligands, there are five compounds with a single oxazoline ring and one compound with a doub- le-oxazoline ring. The ligand with two-oxazoline ring has a C2 axis which was the hotspot in catalytic field. In the application of the designed ligands for the catalytic reaction,the ligands were used in al- lylic alkylation reaction. In the reaction,when 1,3-diphenyl-2-allyl acetate were the substrate,ligand 5a had the optimal yield of 73.5 %.

关 键 词：氮杂环卡宾 噁唑啉 烯丙基烷基化反应 

分 类 号：O626[理学—有机化学]