Nucleophilic Reactivities of Ketene Acetals

The kinetics of the reactions of ketene acetals with benzhydrylium ions have been followed photometrically. The reactions proceed with rate‐determining C−C bond formation that is considerably faster than expected for outer‐sphere electron transfer processes. Structure−reactivity relationships are di...

Full description

Saved in:
Bibliographic Details
Published in:European journal of organic chemistry 2004-07, Vol.2004 (13), p.2791-2796
Main Authors: Tokuyasu, Takahiro, Mayr, Herbert
Format: Article
Language:English
Subjects:
Carbocations
C−C coupling
Kinetics
Linear free energy relationship
Substituent effects
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:The kinetics of the reactions of ketene acetals with benzhydrylium ions have been followed photometrically. The reactions proceed with rate‐determining C−C bond formation that is considerably faster than expected for outer‐sphere electron transfer processes. Structure−reactivity relationships are discussed. The excellent correlations between the observed second‐order rate constants (log k2) and the previously reported electrophilicity parameters (E) of benzhydrylium ions suggest that several of the compounds investigated in this work can be used as reference nucleophiles for the development of electrophilicity scales. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
ISSN:1434-193X
1099-0690
DOI:10.1002/ejoc.200400134