物理化学学报 >> 2004, Vol. 20 >> Issue (09): 1129-1133.doi: 10.3866/PKU.WHXB20040914

研究论文 上一篇    下一篇

吡咯喹啉醌模型化合物与氨亲核加成的理论探讨

王艳花;邹建卫;胡桂香;郑柯文;俞庆森   

  1. 浙江大学化学系,杭州 310027; 浙江大学宁波理工学院分子设计与营养工程市重点实验室,宁波 315104;浙江树人大学生物与环保学院,杭州 310015
  • 收稿日期:2004-02-27 修回日期:2004-05-10 发布日期:2004-09-15
  • 通讯作者: 邹建卫 E-mail:jwzou@css.zju.edu.cn

Theoretical Studies on the Nucleophilic Additions of Mimic Compounds of Pyrroloquinoline Quinone with Ammonia

Wang Yan-Hua;Zou Jian-Wei;Hu Gui-Xiang;Zheng Ke-Wen;Yu Qing-Sen   

  1. Department of Chemistry, Zhejiang University, Hangzhou 310027; Key Laboratory for Molecular Design and Nutrition Engineering of Ningbo City, Ningbo Institute of Technology, Zhejiang University, Ningbo 315104; College of Biology and Environment Protection, Zhejiang Shuren University, Hangzhou 310015
  • Received:2004-02-27 Revised:2004-05-10 Published:2004-09-15
  • Contact: Zou Jian-Wei E-mail:jwzou@css.zju.edu.cn

摘要: 为了揭示辅酶PQQ结构与反应性的关系,在B3LYP/D95(d, p)水平上对一系列PQQ模型化合物及其类似物与氨的亲核加成进行了理论计算.结果表明:对单羰基体系,羰基碳的亲电性对反应能垒有重要的影响;对双羰基体系,过渡态中邻位羰基氧与亲核试剂氨上的H形成的氢键对反应的活化能起着关键的作用;稠合芳香环本身对反应的能垒影响不大,但当稠合杂环的1-位为可提供氢键受体的N原子时,由于N1与氨上H原子间可形成氢键而进一步降低反应的活化能.发现过渡态中被进攻羰基与氨上N原子之间形成的夹角(OCN)与活化能有良好的线性关系.

关键词: 辅酶PQQ(吡咯喹啉醌), 密度泛函理论, 亲核加成, 氢键

Abstract: Nucleophilic additions of a series of mimic compounds of pyrroloquinoline quinone(PQQ) and their analogues with ammonia were investigated at the B3LYP/D95(d, p) level of theory in order to study the relationship between structure and reactivity. It is demonstrated that: (1) for the monocarbonyl system, the electrophilicity of the carbonyl carbon affects significantly the reactive energy barrier; (2) for the biscarbonyl system, the hydrogen bond, formed at the transition state between the hydrogen of the nuclephilic reagent ammonia and the ortho-carbonyl oxygen is crucial for reaction activation energy; (3) while the fused ring has little effect on the reactive barrier, the reaction activation energy can be significantly reduced by the hydrogen bond between H of ammonia and N1 atom in the fused hetercycle. Quantitatively, a good linear correlation has been found between the reaction activation energy and the angle (φ(OCN) ) between the attacked carbonyly and the N atom of the nucleophilic NH3 at the transition state.

Key words: Cofactor PQQ, Density functional theory, Nucleophilic addition,  Hydrogen bond