Acta Phys. -Chim. Sin. ›› 2004, Vol. 20 ›› Issue (09): 1129-1133.doi: 10.3866/PKU.WHXB20040914

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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

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