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The unusual ability of α‐angelicalactone to form adducts: A kinetic approach
Author(s) -
FernándezRodríguez Estrella,
Manso José A.,
PérezPrior M. Teresa,
GarcíaSantos M. del Pilar,
Calle Emilio,
Casado Julio
Publication year - 2007
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.20273
Subject(s) - chemistry , adduct , pyridine , electrophile , lactone , nucleophile , stereochemistry , carcinogen , cleavage (geology) , medicinal chemistry , catalysis , organic chemistry , geotechnical engineering , fracture (geology) , engineering
Since α‐angelicalactone (AAL) substantially inhibits the formation of tumors, here its chemical reactivity was compared with that of carcinogenic lactones. Investigation of the electrophilic potential of AAL was carried out by studying the capacity of this lactone to form adducts with NBP, 4‐( p ‐nitrobenzyl)pyridine, a substrate with nucleophilic characteristics similar to DNA bases. The formation of the AAL–NBP adduct occurs about 900,000‐fold faster than with β‐propiolactone, the most effective carcinogenic lactone (Δ G # 35 = 52 and 87 kJ mol −1 , respectively). A stopped‐flow technique was required for this reaction to be monitored. It was concluded that the formation of AAL–NBP adducts takes place through an entropy‐strain‐catalyzed mechanism caused by early lactone ring cleavage. The kinetic results are consistent with the AAL potential as a chemoprotective agent. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 591–594, 2007