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

被引：32
|
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).
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页码：12225 / 12228
页数：4
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