The Claisen rearrangement of an unusual substrate in chorismate mutase

被引:11
作者
Worthington, SE [1 ]
Krauss, M [1 ]
机构
[1] Ctr Adv Res Biotechnol, Rockville, MD 20850 USA
来源
JOURNAL OF PHYSICAL CHEMISTRY B | 2001年 / 105卷 / 29期
关键词
D O I
10.1021/jp010228o
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The calculated reaction path for an unusual substrate of chorismate mutase (Bacillus subtilis) is found to be completely comparable to that of the native chorismate. In the unusual substrate, the cyclohexadienyl ring in chorismate is replaced by dihydropyridine. Previous theoretical calculations of the native reaction path provide the basis for predicting that the interactions of the unusual reactant in the active site are electronically analogous to the native. Three unusual substrates are obtained by replacing each of the C-H moieties in the cyclohexadienyl ring by a nitrogen atom. This substitution does not substantially alter the electronic characteristics of the ring both with regard to the catalytic activation by the active site and the interaction with hydrophobic groups in the active site. The activation energies and optimized structures along the reaction path are obtained for the tautomers of the unusual reactant and product. The possibility of ultimately obtaining an unusual amino acid by this pathway is discussed.
引用
收藏
页码:7096 / 7098
页数:3
相关论文
共 11 条
[1]   The Protein Data Bank [J].
Berman, HM ;
Westbrook, J ;
Feng, Z ;
Gilliland, G ;
Bhat, TN ;
Weissig, H ;
Shindyalov, IN ;
Bourne, PE .
NUCLEIC ACIDS RESEARCH, 2000, 28 (01) :235-242
[2]   THE MONOFUNCTIONAL CHORISMATE MUTASE FROM BACILLUS-SUBTILIS - STRUCTURE DETERMINATION OF CHORISMATE MUTASE AND ITS COMPLEXES WITH A TRANSITION-STATE ANALOG AND PREPHENATE, AND IMPLICATIONS FOR THE MECHANISM OF THE ENZYMATIC-REACTION [J].
CHOOK, YM ;
GRAY, JV ;
KE, HM ;
LIPSCOMB, WN .
JOURNAL OF MOLECULAR BIOLOGY, 1994, 240 (05) :476-500
[3]   An effective fragment method for modeling solvent effects in quantum mechanical calculations [J].
Day, PN ;
Jensen, JH ;
Gordon, MS ;
Webb, SP ;
Stevens, WJ ;
Krauss, M ;
Garmer, D ;
Basch, H ;
Cohen, D .
JOURNAL OF CHEMICAL PHYSICS, 1996, 105 (05) :1968-1986
[4]  
Dewick PM, 1998, NAT PROD REP, V15, P17
[5]   Crystal structures of Paracoccus denitrificans aromatic amino acid aminotransferase:: A substrate recognition site constructed by rearrangement of hydrogen bond network [J].
Okamoto, A ;
Nakai, Y ;
Hayashi, H ;
Hirotsu, K ;
Kagamiyama, H .
JOURNAL OF MOLECULAR BIOLOGY, 1998, 280 (03) :443-461
[6]   GENERAL ATOMIC AND MOLECULAR ELECTRONIC-STRUCTURE SYSTEM [J].
SCHMIDT, MW ;
BALDRIDGE, KK ;
BOATZ, JA ;
ELBERT, ST ;
GORDON, MS ;
JENSEN, JH ;
KOSEKI, S ;
MATSUNAGA, N ;
NGUYEN, KA ;
SU, SJ ;
WINDUS, TL ;
DUPUIS, M ;
MONTGOMERY, JA .
JOURNAL OF COMPUTATIONAL CHEMISTRY, 1993, 14 (11) :1347-1363
[7]   COMPACT EFFECTIVE POTENTIALS AND EFFICIENT SHARED-EXPONENT BASIS-SETS FOR THE 1ST-ROW AND 2ND-ROW ATOMS [J].
STEVENS, WJ ;
BASCH, H ;
KRAUSS, M .
JOURNAL OF CHEMICAL PHYSICS, 1984, 81 (12) :6026-6033
[8]   RELATIVISTIC COMPACT EFFECTIVE POTENTIALS AND EFFICIENT, SHARED-EXPONENT BASIS-SETS FOR THE 3RD-ROW, 4TH-ROW, AND 5TH-ROW ATOMS [J].
STEVENS, WJ ;
KRAUSS, M ;
BASCH, H ;
JASIEN, PG .
CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE, 1992, 70 (02) :612-630
[9]   Effective fragment potentials and the enzyme active site [J].
Worthington, SE ;
Krauss, M .
COMPUTERS & CHEMISTRY, 2000, 24 (3-4) :275-285
[10]  
WORTHINGTON SE, UNPUB J PHYS CHEM B