化学学报 ›› 2006, Vol. 64 ›› Issue (9): 959-962. 上一篇    

研究简报

N-磷酰化氨基酸生成五配位磷中间体过程中氨基酸侧链立体化学效应的理论研究

赵丽娇1,钟儒刚*,1,2,甄岩1,赵玉芬2   

  1. (1北京工业大学生命科学与生物工程学院 北京 100022)
    (2生命有机磷化学及化学生物学教育部重点实验室 清华大学化学系 北京 100084)
  • 收稿日期:2005-11-08 修回日期:2006-01-13 出版日期:2006-05-15 发布日期:2006-05-15
  • 通讯作者: 钟儒刚

Stereochemical Effect of the Amino Acid Side Chain on the Formation of Penta-coordinate Phosphorus Intermediates from N-Phosphorylamino acid: A Theoretical Study

ZHAO Li-Jiao1, ZHONG Ru-Gang*,1,2, ZHEN Yan1, ZHAO Yu-Fen2   

  1. (1 College of Life Science and Bioengineering, Beijing University of Technology, Beijing 100022)
    (2 Key Laboratory of Bioorganic Phosphorus Chemistry & Chemical Biology, Ministry of Education,
    Department of Chemistry, Tsinghua University, Beijing 100084)
  • Received:2005-11-08 Revised:2006-01-13 Online:2006-05-15 Published:2006-05-15
  • Contact: ZHONG Ru-Gang

用密度泛函(DFT)方法在B3LYP/6-311G(d,p)水平上对N-磷酰化氨基酸生成五配位磷酸羧酸混酐(IMCPA)反应中手性氨基酸残基侧链的立体化学效应进行了研究. 模拟了氨基酸残基上羧基氧原子从磷酰基的不同侧面进攻磷原子从而形成不同构型五配位磷中间体的反应途径, 探讨了IMCPA生成过程中的立体选择性.

关键词: N-磷酰化氨基酸, 生命起源, 立体化学效应, DFT

The stereochemical effect of the chiral amino acid residues on the formation of penta-coordinate phosphorus intermolecular mixed carboxylic-phosphoric anhydride (IMCPA) from N-phosphorylamino- acids is studied with density functional theory (DFT) calculations at B3LYP/6-311G(d,p) level. The reaction pathways for the formation of penta-coordinate phosphorus intermediates with different configurations through the carboxyl oxygen on amino acid group attacking the phosphoryl group from different directions are simulated and the stereoselectivity in the formation of IMCPA is discussed.

Key words: N-phosphorylamino acid, origin of life, stereochemical effect, DFT