HYDROLYSE ACIDO-CATALYSEE D'UN SULFURE DE DIENYLE APPLICATION A LA SYNTHESE DE LA gamma-DAMSCONE

Article abstract of DOI:10.1016/S0040-4020(01)90341-2

A new synthetic route to γ-Damascone 1 starting with methyl-γ-dithiocyclogeranate 2 is described.Addition of HMPT was found necessary to perform the carbophilic addition of allylmagnesium bromide on dithioester 2.A dienylsulfide, 6,6-dimethyl-2-methylene-(1-methylthio-1,3-butadiene)-1-yl cyclohexane 3 resulted from this addition, and not the expected dithioketal.Following a number of described conditions, hydrolysis of 3 to γ-damascone 1 proved to be unsatisfactory.These initial attempts but showed the necessity for an acidic medium.This finding allowed the development of a new, very mild method of hydrolysis of dienylsulfides to unsaturated ketones.