Linear free energy relationships and kinetic isotope effects reveal the chemistry of the Ado 2′-OH group

被引：5

作者：

Changalov, Mohamed M. ^{[1
]}

Petkov, Dimiter D. ^{[1
]}

机构：

[1] Bulgarian Acad Sci, Inst Organ Chem, Lab BioCatalysis, BU-1113 Sofia, Bulgaria

来源：

TETRAHEDRON LETTERS | 2007年 / 48卷 / 13期

关键词：

D O I：

10.1016/j.tetlet.2007.01.139

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Using kinetic isotope effects (KIE) and Hammett correlations, we show that the main role of the adenosine 2'-OH group on deprotonation by the non nucleophilic base DBU during external acyl group transfer is to generate enhanced electron density on the attacking nucleophile through ionization. The small primary KIEs (1.2 and 1.6) and the large Hammett reaction constants (+2.25 and +3.19) obtained for the ethanolysis of 2'/3'-O-p-substituted benzoyl 5'-O-trityl adenosines and 2'-deoxyadenosines are consistent with an A(N) + D-N reaction mechanism. The implications of our results are discussed in terms of chemical contributions of the 2'-OH group in the ribosome catalysis of peptide bond formation. (c) 2007 Elsevier Ltd. All rights reserved.

引用

页码：2381 / 2384

页数：4

共 33 条

[1] Activation of oxygen nucleophiles in enzyme catalysis [J].

Anderson, Vernon E. ;

Ruszczycky, Mark W. ;

Harris, Michael E. .

CHEMICAL REVIEWS, 2006, 106 (08) :3236-3251

[2]

BARTA A, 1996, RIBOSOMAL RNA GROUP, P35

[3] CONCERTEDNESS IN ACYL GROUP TRANSFER IN SOLUTION - A SINGLE TRANSITION-STATE IN ACETYL GROUP TRANSFER BETWEEN PHENOLATE ION NUCLEOPHILES [J].

BASAIF, S ;

LUTHRA, AK ;

WILLIAMS, A .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (21) :6362-6368

[4] CONCERTED ACETYL GROUP TRANSFER BETWEEN SUBSTITUTED PHENOLATE ION NUCLEOPHILES - VARIATION OF TRANSITION-STATE STRUCTURE AS A FUNCTION OF SUBSTITUENT [J].

BASAIF, S ;

LUTHRA, AK ;

WILLIAMS, A .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (07) :2647-2652

[5] AN OPEN TRANSITION-STATE IN CARBONYL ACYL GROUP TRANSFER IN AQUEOUS-SOLUTION [J].

BASAIF, SA ;

COLTHURST, M ;

WARING, MA ;

WILLIAMS, A .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1991, (12) :1901-1908

[6] MECHANISMS OF CATALYSIS OF NUCLEOPHILIC REACTIONS OF CARBOXYLIC ACID DERIVATIVES [J].

BENDER, ML .

CHEMICAL REVIEWS, 1960, 60 (01) :53-113

[7] Peptide bond formation does not involve acid-base catalysis by ribosomal residues [J].

Bieling, P ;

Beringer, M ;

Adio, S ;

Rodnina, MV .

NATURE STRUCTURAL & MOLECULAR BIOLOGY, 2006, 13 (05) :423-428

[8] DIRECT OBSERVATION OF SIMPLE TETRAHEDRAL INTERMEDIATES [J].

CAPON, B ;

GHOSH, AK ;

GRIEVE, DMA .

ACCOUNTS OF CHEMICAL RESEARCH, 1981, 14 (10) :306-312

[9] 2′/3′-O-peptidyl adenosine as a general base catalyst of its own external peptidyl transfer:: Implications for the ribosome catalytic mechanism [J].

Changalov, MM ;

Ivanova, GD ;

Rangelov, MA ;

Acharya, P ;

Acharya, S ;

Minakawa, N ;

Földesi, A ;

Stoineva, IB ;

Yomtova, VM ;

Roussev, CD ;

Matsuda, A ;

Chattopadhyaya, J ;

Petkov, DD .

CHEMBIOCHEM, 2005, 6 (06) :992-996

[10] Mechanisms of phosphoryl and acyl transfer [J].

Cleland, WW ;

Hengge, AC .

FASEB JOURNAL, 1995, 9 (15) :1585-1594

← 1 2 3 4 →