Oxygen chiral phosphate esters.
Oxygen chiral phosphate esters.
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氧手性磷酸酯。
DOI：
10.1002/9780470123010.ch4
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发表时间：
1983
期刊：
影响因子：
--
通讯作者：
Mehdi,S
中科院分区：
文献类型：
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作者：
Gerlt,JA;Coderre,JA;Mehdi,S
催化磷酰基和核苷酸基转移反应的酶在生物化学和分子生物学中具有根本重要性，酶学家投入了大量精力来阐明这些反应的机制 (1)。本综述描述了立体化学技术的开发和应用，该技术已用于确定磷酰基或核苷酸基的转移是否发生在被转移的磷原子处构型反转或保留的情况下。由于现在人们认为五配位中间体（假旋转，2）的配体重组过程在酶催化反应中并不重要，因此获得的立体化学信息已用于推断磷原子处发生的亲核置换的数量：构型反转意味着一个键断裂反应，这与磷酰基或核苷酸基团从供体到受体的直接转移一致，以及构型的保留意味着两个键破坏反应，
Enzymes that catalyze phosphoryl and nucleotidyl transfer reactions are of fundamental importance in biochemistry and molecular biology, and enzymologists have devoted considerable effort to the elucidation of the mechanisms of these reactions (1). This review describes the development and application of stereochemical techniques which have been used to determine whether the transfer of a phosphoryl or nucleotidyl group occurs with inversion or retention of configuration at the phosphorus atom being transferred. Since it is now accepted that ligand reorganization processes of pentacoordinate intermediates (pseudorotation, 2) are unimportant in enzyme-catalyzed reactions, the stereochemical information obtained has been used to deduce the number of nucleophilic displacements that occur at the phosphorus atom: inversion of configuration implying one bond breaking reaction, which is consistent with the direct transfer of a phosphoryl or nucleotidyl group from a donor to acceptor, and retention of configuration implying two bond breaking reactions,