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DOI: 10.1055/sos-SD-221-00221

Beccalli, E. M.; Bonetti, A.; Mazza, A.Science of Synthesis: Metal-Catalyzed Cyclization Reactions, (20161445.

Carbonylation of secondary ω-arylalkylamines 139 by direct aromatic metalation affords five- and six-membered benzolactams 140. The reaction is carried out under phosphine-free catalytic conditions using palladium(II) acetate as catalyst and copper(II) acetate as oxidant under an atmosphere of carbon monoxide gas containing air (Scheme 61).[‌90‌] Five-membered rings are formed 11 times faster than six-membered rings. The electronic effects of aryl substituents have also been examined. In the case of possible regioselectivity, two regioisomers are obtained. By contrast, carbonylation of primary amines under the same conditions does not produce benzolactams, but rather ureas in good yields.

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