Transition-State Structure for the Quintessential SN2 Reaction of a Carbohydrate: Reaction of α-Glucopyranosyl Fluoride with Azide Ion in Water

被引：34

作者：

Chan, Jefferson ^{[1
]}

Sannikova, Natalia ^{[1
]}

Tang, Ariel ^{[1
]}

Bennet, Andrew J. ^{[1
]}

机构：

[1] Simon Fraser Univ, Dept Chem, Burnaby, BC V5A 1S6, Canada

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2014年 / 136卷 / 35期

基金：

加拿大自然科学与工程研究理事会;

关键词：

ISOTOPE FRACTIONATION; AQUEOUS-SOLUTION; METHYL CARBON; PRIMARY C-13; CYANIDE ION; COMMON ION; HYDROLYSIS; OXOCARBENIUM; ACID; SOLVOLYSIS;

D O I：

10.1021/ja506092h

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We report that the S(N)2 reaction of alpha-D-glucopyranosyl fluoride with azide ion proceeds through a loose (exploded) transition-state (TS) structure. We reached this conclusion by modeling the TS using a suite of five experimental kinetic isotope effects (KIEs) as constraints for the calculations. We also report that the anomeric C-13-KIE is not abnormally large (k(12)/k(13) = 1.024 +/- 0.006), a finding which is at variance with the previous literature value (Zhang et al. J. Am. Chem. Soc. 1994, 116, 7557).

引用

页码：12225 / 12228

页数：4

共 47 条

[1] LIFETIMES OF OXOCARBENIUM IONS IN AQUEOUS-SOLUTION FROM COMMON ION INHIBITION OF THE SOLVOLYSIS OF ALPHA-AZIDO ETHERS BY ADDED AZIDE ION [J].

AMYES, TL ;

JENCKS, WP .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (20) :7888-7900

[2] The preferred all-gauche conformations in 3-fluoro-1,2-propanediol [J].

Andrade, Laize A. F. ;

Silla, Josue M. ;

Duarte, Claudimar J. ;

Rittner, Roberto ;

Freitas, Matheus P. .

ORGANIC & BIOMOLECULAR CHEMISTRY, 2013, 11 (39) :6766-6771

[3]

[Anonymous], REACTION RATES ISOTO

[4] REACTIONS OF ANIONIC NUCLEOPHILES WITH ALPHA-D-GLUCOPYRANOSYL FLUORIDE IN AQUEOUS-SOLUTION THROUGH A CONCERTED, A(N)D(N) (S(N)2) MECHANISM [J].

BANAIT, NS ;

JENCKS, WP .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (21) :7951-7958

[5] GENERAL-ACID AND GENERAL-BASE CATALYSIS OF THE CLEAVAGE OF ALPHA-D-GLUCOPYRANOSYL FLUORIDE [J].

BANAIT, NS ;

JENCKS, WP .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (21) :7958-7963

[6] CARBON-14 KINETIC ISOTOPE EFFECTS .3. THE HYDROLYSIS OF 2-CHLORO-2-METHYLPROPANE-2-C14 [J].

BENDER, ML ;

BUIST, GJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1958, 80 (16) :4304-4307

[7] Mechanisms of glycopyranosyl and 5-thioglycopyranosyl transfer reactions in solution [J].

Bennet, AJ ;

Kitos, TE .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 2002, (07) :1207-1222

[8] O-18 AND SECONDARY H-2 KINETIC ISOTOPE EFFECTS CONFIRM THE EXISTENCE OF 2 PATHWAYS FOR ACID-CATALYZED HYDROLYSES OF ALPHA-ARABINOFURANOSIDES [J].

BENNET, AJ ;

SINNOTT, ML ;

WIJESUNDERA, WSS .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1985, (08) :1233-1236

[9] COMPLETE KINETIC ISOTOPE EFFECT DESCRIPTION OF TRANSITION-STATES FOR ACID-CATALYZED HYDROLYZES OF METHYL ALPHA-GLUCOPYRANOSIDES AND BETA-GLUCOPYRANOSIDES [J].

BENNET, AJ ;

SINNOTT, ML .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1986, 108 (23) :7287-7294

[10]

BERGSON G, 1977, CHEM SCRIPTA, V11, P25

← 1 2 3 4 5 →