C. Di Vitta et al., New reductive addition of hard nucleophiles to 6,7-bis(methylsulfanyl)-1,4-dihydro-1,4-methanonaphthalene-5,8-dione, J CHEM S P1, (21), 2000, pp. 3692-3694
A new reaction mode of 6,7-bis(methylsulfanyl)-1,4-dihydro-1,4-methanonapht
halene-5,8-dione 1 with the hard nucleophiles sodium benzene- or methane-su
lfinate and cyanide, in DMSO, at room temperature, leads to the unexpected
hydroquinonoid products 3a-c. All the data are in agreement with a mechanis
tic pathway involving the initial attack of the hard nucleophile onto the h
ard carbonyl group, followed by a symbiotic re-attack of the oxygen on the
incoming group. In the case of soft nucleophiles, reaction on the olefinic
carbon of the enedione system is preferential.