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Dioxirane Oxidation of Furocoumarins and Naphthofurans Preparation of the Psoralen Epoxides

✍ Scribed by Adam, Waldemar ;Sauter, Markus

Publisher
John Wiley and Sons
Year
1994
Tongue
English
Weight
487 KB
Volume
1994
Category
Article
ISSN
0947-3440

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✦ Synopsis

Abstract

Methyl(trifluoromethyl)dioxirane oxidation of natural psoralen (1a) and 8‐methoxypsoralen (8‐MOP, 1b) and dimethyldioxirane oxidation of some related 2,3‐substituted furocoumarins 1c–e at subambient temperature afforded the corresponding labile epoxides 2a–e. The reaction of acetylated 2,3‐dimethylnaphthofurans 1f,g with dimethyldioxirane afforded the corresponding quinone methides 3f, g, derived from the valence‐isomeric epoxides 2f,g. Cycloaddition of ethyl vinyl ether to the quinone methides 3b, c led to the benzopyrans 5b, c. In methanol at −50°C, the 8‐MOP epoxide (2a) was converted by nucleophilic attack into the corresponding adduct 4b. The latter result demonstrates that the psoralen epoxides may serve as powerful alkylating agents and provides a possible chemical basis for their observed genotoxicity due to adduct formation by nucleophilic attack of DNA. magnified image

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