葛伟伟,孔凡华,黄力华.手性磷酰胺类化合物不对称催化合成α-芳基丙醇类化合物[J].分子催化,2022,36(1):22-31
手性磷酰胺类化合物不对称催化合成α-芳基丙醇类化合物
Asymmetric Synthesis of α -Arylpropanol Compounds by Chiral Phosphoramide Compounds Catalysts
投稿时间:2021-11-19  修订日期:2021-12-20
DOI:10.16084/j.issn1001-3555.2022.01.003
中文关键词:  手性磷酰胺类化合物  不对称催化  α-芳基丙醇
英文关键词:chiral phosphoramide compound  asymmetric catalysis  α -arylpropano
基金项目:山东省自然科学基金面上项目(ZR2021ME187
作者单位E-mail
葛伟伟 临沂市生态环境监控中心, 山东 临沂 276001  
孔凡华 山东临沂生态环境监测中心, 山东 临沂 276001  
黄力华 临沂大学, 山东 临沂 276005 huanglihua328@163.com 
摘要点击次数: 864
全文下载次数: 619
中文摘要:
      对一系列磷酰胺类化合物进行了考察,发现以芳香醛类化合物与二乙基锌作为底物,手性磷酰胺类化合物4a(N-(1R,2R)-2-(异丙基氨基)-1,2-二苯基乙基)-P,P-二苯基次膦酰胺)作为催化剂,通过发生不对称还原反应合成具有生理活性的α-芳基丙醇类化合物.手性磷酰胺类化合物合成所使用的起始物料不仅廉价易得,而且催化效率也比较高.在优化出的最优反应条件下,4a的使用量为10%(摩尔分数),可以高选择性、高产率地催化合成手性α-芳基丙醇类化合物,且手性磷酰胺类化合物可以回收利用.通过反应机理研究,提出催化反应过程中形成的含有四元、六元过渡态以及空间位阻作用的中间态是导致所得α-芳基丙醇类化合物有较高的ee值的决定步骤.
英文摘要:
      Chiral α -arylpropanol compounds with important biological activity were synthesized with high yield and catalytic efficiency from thiophosphoramide 4a(N((-1R,2R)-2(-isopropylamino)-1,2-diphenylethyl)-P,Pdiphenylphosphinicamide) as catalyst, aromatic aldehydes and diethylzinc as reactants by catalytic asymmetric reduction reaction. The raw materials for 4a are cheap and easy to obtain. Under the optimal conditions(the usage amount of 4a is 10%(Mole fraction)), chiral α -arylpropanol compounds can be synthesized with high yield and e.e. value. 4a was very convenient to recycle and reuse in this system. It is proposed that the intermediate states containing quaternary and six-member transition states and steric hindrance formed during the catalytic reactionare beneficial to improve the enantioselectivity of the reaction.
HTML  查看全文  查看/发表评论  下载PDF阅读器