REGIOSELECTIVE PALLADIUM(II)-CATALYZED SYNTHESIS OF 5-MEMBERED OR 7-MEMBERED RING LACTONES AND 5-MEMBERED, 6-MEMBERED OR 7-MEMBERED RING LACTAMS BY CYCLOCARBONYLATION METHODOLOGY

2-Allylphenols react with carbon monoxide and hydrogen in the presence of catalytic quantities of a cationic palladium(II) complex [(PCy(3)) (2)Pd(H)(H2O)](BF4-)-B-+ or palladium acetate and 1,4-bis(diphenylphos phino)butane, affording five- or seven-membered ring lactones (bicycli c, tricyclic, and pentacyclic) as the principal products, often in exc ellent yields. Use of 2-aminostyrenes as reactants and catalytic quant ities of palladium acetate and tricyclohexylphosphine, affords five-me mbered ring lactams in high yield and selectivity. Bicyclic and tricyc lic heterocycles containing six-membered ring lactams can be synthesiz ed from the reaction of 2-allylanilines with CO/ H-2 using the catalyt ic system Pd(OAc)(2)/PPh(3), while use of 1,4-bis(diphenylphosphino)bu tane instead of PPh(3) in the latter process results in the formation of the seven-membered lactams benzazepinones in good yield, The regioc hemical control depends on the nature of the palladium catalyst, the r elative pressures of the gases, and the solvent.