镁-双噁唑啉络合物催化3,5-二甲基-N-α,β-不饱和酰基吡唑的不对称共轭氰化反应研究  

Study on Asymmetric Conjugate Cyanation of 3,5-Dimethyl-N-α,β-unsaturated Acylpyrazole Catalyzed by Magnesium-Bisoxazoline Complex

作　　者：刘云姝 赵国栋[1] 武文菊 王云泽 喻艳超 由君[1] 刘波[1] Liu Yunshu;Zhao Guodong;Wu Wenju;Wang Yunze;Yu Yanchao;You Jun;Liu Bo(Key Laboratory of Green Chemical Engineering and Technology of Heilongjiang Province,School of Materials Science and Chemical Engineering,Harbin University of Science and Technology,Harbin 150040)

机构地区：[1]哈尔滨理工大学材料科学与化学工程学院,黑龙江省绿色化工技术重点实验室,哈尔滨150040

出　　处：《有机化学》2022年第1期208-217,共10页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(No.22008045);黑龙江省普通本科高等学校青年创新人才培养计划(No.UNPYSCT-2020199)资助项目。

摘　　要：报道了镁-双噁唑啉络合物体系催化的TMSCN与3,5-二甲基-N-α,β-不饱和酰基吡唑的不对称共轭氰化反应.考察了BOX配体结构、配体与金属比例、温度、溶剂等对反应的影响.研究结果表明,使用双苄基取代的双噁唑啉配体与二丁基镁(物质的量比为2∶1)在1,2-二氯乙烷中原位生成手性催化剂,催化剂用量为10 mol%,反应温度为-32℃,不对称共轭氰化反应催化效果最佳.将上述催化方法应用于一系列3,5-二甲基-N-α,β-酰基吡唑衍生物,绝大部分以90%以上的产率和中等以上的对映选择性获得相应的目标产物.The asymmetric conjugate cyanation reaction of TMSCN with 3,5-dimethyl-N-α,β-unsaturated acylpyrazole catalyzed by magnesium-bisoxazoline complex was studied.The effects of BOX ligand structure,ligand to metal ratio,temperature,solvent,etc.on the reaction were investigated.The results showed that when bis-benzyl substituted bisoxazoline ligand and dibutylmagnesium(molar ratio 2∶1)were used to generate chiral catalyst in situ in 1,2-dichloroethane,the amount of catalyst was 10 mol%,and the reaction temperature was-32℃,and the catalytic effect of asymmetric conjugate cyanation reaction was the best.The catalytic method above was applied to the conjugate cyanation reaction of a series of 3,5-dimethyl-N-α,β-unsaturated acyl pyrazole derivatives,most of the corresponding target products could be obtained with more than 90%yield and moderate to good enantioselectivities.

关 键 词：双噁唑啉 三甲基氰硅烷 3 5-二甲基-N-α β-不饱和酰基吡唑 不对称共轭氰化 

分 类 号：O621.251[理学—有机化学]