锰催化烯烃的反马氏硼氢化实验研究  

Experimental Study on Mn-catalyzed Anti-Markovian Hydroboration of Olefins

作　　者：宋吉亮 张雨来 王娇 SONG Jiliang;ZHANG Yulai;WANG Jiao(School of Chemical Engineering,Dalian University of Technology,Panjin 124221,Liaoning,China;Panjin Institute of Industrial Technology,Liaoning Key Laboratory of Chemical Additive Synthesis and Separation,Dalian University of Technology,Panjin 124221,Liaoning,China)

机构地区：[1]大连理工大学化工学院,辽宁盘锦124221 [2]大连理工大学盘锦产业技术研究院,辽宁省化学助剂合成与分离省重点实验室,辽宁盘锦124221

出　　处：《实验室研究与探索》2023年第3期9-12,共4页Research and Exploration In Laboratory

基　　金：国家自然科学基金项目(21872015);辽宁省化学助剂合成与分离省重点实验室开放课题基金资助项目(ZJKF2015,ZJKF2011);大连理工大学大学生创新创业训练项目(20221014110030)。

摘　　要：研究了锰催化烯烃的反马氏硼氢化反应,以苯乙烯和联硼酸频那醇酯为模型反应的底物,观察了配体、催化剂、溶剂、添加剂、氢源、温度以及反应时间对反应产率的影响。实验结果表明,在四氢呋喃溶液中氯化锰为催化剂、叔丁醇钾为添加剂、甲醇为氢源、联吡啶为配体时,以60℃反应10 h产率最高,得到分离收率为84.6%的反马氏硼氢化产物;产物的结构通过核磁共振氢谱、碳谱及红外光谱分析等表征方法得以确认。此反应催化体系具有原料绿色易得、条件温和、实验操作简单等优点。同时,该反应首次以锰盐/配体的催化体系实现了烯烃反马氏硼氢化反应,得到了相应的有机硼化合物,也为合成大分子化合物及药物中间体提供了新思路和新途径。Using pinacol diborate as boron source,manganese catalyzed anti martensine borohydride of olefins is studied.The effects of ligands,catalysts,solvents,additives,hydrogen sources,temperature and reaction time on the yield of styrene and pinacol diborate are investigated.The experimental results showed that the highest yield is obtained when manganese chloride is used as catalyst,potassium tert-butanol as additive,methanol as hydrogen source,bipyridine as ligand,and tetrahydrofuran solution is used for reaction for 10 hours at 60℃.The separation yield of anti-martensite borohydride is 84.6%;The structure of the product is confirmed by 1H NMR,13C NMR and IR spectroscopy.The catalytic reaction system has the advantages of green raw materials,mild conditions and simple experimental operation.At the same time,the anti Mahalanobic hydrogenation of olefins is realized for the first time in the manganese salt/ligand catalytic system,and the corresponding organic boron compounds are obtained.This reaction also provides new ideas and new ways for the synthesis of macromolecular compounds and pharmaceutical intermediates.

关 键 词：反马氏硼氢化反应 烯烃 联硼酸频那醇酯 锰催化剂 

分 类 号：O621.3[理学—有机化学] O69[理学—化学] TQ032.4[化学工程]