The terminal alkene of D first undergoes Wacker oxidation, giving the side chain . Alkene coordination to Pd(II), water attack, proton transfers and beta-hydride elimination give the ketone. Copper and oxygen regenerate the active palladium oxidation state.
Base removes a proton from the terminal methyl of that ketone. Its enolate attacks the neighboring aromatic aldehyde intramolecularly, closing a six-membered ring. Dehydration gives a conjugated cyclohexadienone-type intermediate, and keto-enol tautomerism furnishes aromatic naphthol E. The retained methoxy and MOM-protected oxygen groups follow the original aromatic-carbon positions.
F is the O-allyl ether of E. Carbonate forms the naphthoxide and allyl bromide undergoes an SN2 reaction at its terminal carbon. Heating F then causes a [3,3]-Claisen rearrangement: the O–allyl bond breaks, the terminal allyl carbon bonds to the adjacent naphthalene C1, and the phenolic carbon temporarily becomes a ketone. Rearomatization gives G, with a free phenolic OH and a C1 allyl group. The C1 position gives the favored alpha-substituted naphthol and avoids the alternative less favorable annulation pattern.
The final step is a dearomative Michael addition, not a Nef conversion of the nitro group. Hydrogen bonding from the thiourea activates nitroethylene. The nucleophilic C1 resonance form of G attacks the terminal carbon of , and proton transfer converts the nitronate to a 2-nitroethyl substituent. The phenolic carbon becomes a ketone.
H is the corresponding 1-allyl-1-(2-nitroethyl)naphthalen-2-one, retaining the methoxy and MOM substituents of G. The second ring now has a C2=O group and a C3=C4 bond, while the other ring remains aromatic. The reported C signal near ppm is consistent with that newly formed ketone. Related dearomative additions establish this reaction class.[ref]
C1 is now an all-carbon quaternary stereocenter bearing both allyl and 2-nitroethyl groups. Both the drawn thiourea and the starting materials are achiral, so H is racemic. A chiral catalyst would be needed to select one absolute configuration.
O-allyl intermediate and dearomative Michael-addition product
. Details. 