An unexpected pathway in the palladium-catalysed chemistry of allyl carbonates; the transfer of allyloxycarbonyl groups without loss of CO2

Abstract

Treatment of hindered steroidal alcohols 4 and 11 with allyl ethyl carbonate in the presence of palladium complexes led to the steroidal allyl carbonates 10 and 12, as opposed to the expected allyl ethers; these reactions are exceptional in that carbon dioxide is not lost from the carbonate, and suggest an alternative to the generally accepted mechanism for the interaction of Pd catalysts with allyl carbonates.