Nitration versus nitrosation chemistry of menthofuran: Remarkable fragmentation and dimerization pathways and expeditious entry into dehydromenthofurolactone

Maria De Lucia, Francesco Mainieri, Luisella Verotta, Massimo Maffei, Lucia Panzella, Orlando Crescenzi, Alessandra Napolitano, Vincenzo Barone, Giovanni Appendino, Marco D'Ischia

Risultato della ricerca: Contributo su rivistaArticolo in rivistapeer review

Abstract

(Chemical Equation Presented) The reaction chemistry of menthofuran (1), a toxic furan terpenoid from various mint oils, with nitric acid and nitrous acid has been investigated. Treatment of 1 with nitric acid afforded a 1:1 mixture of the bisfuran derivatives 5 and 6, resulting from the unexpected cleavage of the furan into two carbonyl fragments (3-methylcyclohexanone and hydroxyacetone) and their subsequent trapping by unreacted 1. Under conditions of high dilution, the nitrofuran derivative 7 was formed instead as the major reaction product. During investigation of this chemistry, it was found that oxidation of 1 with DDQ led to the important fragrant monoterpenoid 4 [dehydromenthofurolactone (anhydro Woodward-Eastman lactone)] in 44% yield. Exposure of 1 to nitrite ions at pH 3 afforded a completely different type of products, encompassing the known lactone 14, the lactam 15, and the remarkable dimer 16, bearing a N-hydroxy-2-pyrrolinone moiety linked to a nitrooximinofuran unit by an oxygen bridge. By using a combined spectroscopic and DFT approach, the constitution and configuration of 16 could be determined. These results fill a gap in the chemistry of furan compounds and describe routes to menthofuran-derived scaffolds of potential synthetic and biomedical relevance.

Lingua originaleInglese
pagine (da-a)10123-10129
Numero di pagine7
RivistaJournal of Organic Chemistry
Volume72
Numero di pubblicazione26
DOI
Stato di pubblicazionePubblicato - 21 dic 2007
Pubblicato esternamente

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