Ruthenium-Catalyzed Nucleophilic Allylic Substitution Reactions from β-Silylated Allylic Carbonates

The trans addition of HSiEt3 to propargylic ethyl carbonates catalyzed by the ruthenium complex [Ru(C5Me5)(MeCN)(3)][PF6], 1, leads to H2C=C(SiEt3)CH(R)OCO2Et (R = H, Me, Pr-n, or Ph) derivatives as allylic substrates for Subsequent ruthenium-catalyzed nucleophilic allylic Substitution reactions. Ruthenium catalysts based on a [Ru(C5Me5)(2-quinolinecarboxylato)] or [Ru(C5Me5)(2,2'-bipyridine)](+) fragment are more efficient than 1 for access to various H2C=C(SiEt3)CH(R)Nufunctionalized vinylsilanes (R = H, Me; NuH = secondary amine, phenol, dimethylmalonate, methanol). New [Ru(C5Me5)(2-quinolinecarboxylato)(eta(3-)allyl)](+) cationic ruthenium(IV) intermediates are characterized, and experiments using a deuteriurn-labelcd allylic carbonate provide evidence for a regioselectivity arising from the presence of the 2-quinolinecarboxylato (N,O)-chelate.