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Effect of neighbouring amide group bulkiness on anchimerically assisted ether bond cleavage: Part 7
Author(s) -
Arcelli Antonio,
Porzi Gianni,
Rinaldi Samuele,
Sandri Sergio
Publication year - 2004
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.726
Subject(s) - chemistry , hydrolysis , ether , amide , ether cleavage , vicinal , peptide bond , leaving group , bond cleavage , medicinal chemistry , stereochemistry , organic chemistry , enzyme , catalysis
The effect of the bulkiness of the amide group vicinal to the ether bond on the acid hydrolysis rate of substrates 1b – d was investigated. The kinetic data showed that increased bulkiness of the acyl group has a considerable effect on the reaction rate, accelerating the anchimerically assisted hydrolytic process of the ether bond. A different mechanism is proposed for 1d , which is supported by the thermodynamic activation parameters values. The hydrolysis rate of 1d is about 3 × 10 5 ‐fold higher than that of the reference compound. Copyright © 2004 John Wiley & Sons, Ltd.