Novel synthesis of 3-carboxamidolactam derivatives via palladium-catalysed aminocarbonylation

Kollár, László and Takács, Attila (2018) Novel synthesis of 3-carboxamidolactam derivatives via palladium-catalysed aminocarbonylation. TETRAHEDRON, 74. pp. 6116-6128. ISSN 0040-4020

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Abstract

Aminocarbonylation of alkenyl and (hetero)aryl iodides using medium-sized 3-aminolactams as N-nucleophiles was carried out in the presence of in situ palladium(0) catalysts. While the iodoalkenes were converted to the corresponding carboxamide under mild reaction condition (1 bar of CO, 50 C) by using Pd(OAc)2/PPh3 catalysts, the iodobenzene shown decreased reactivity (39% conversion after 2 days) under the similar reaction conditions in the presence of 3-aminoazepan-2-one. The reactivity of iodobenzene and other iodo(hetero)aromatic substrates was increased with 3-aminoazepan-2-one under high (40 bar) carbon monoxide pressure, but the hemoselectivity was shifted towards the 2-ketocarboxamides formed via double carbon monoxide insertion (except 2-iodopyridine). Changing triphenylphosphine to Xantphos, the expected carboxamides were chemoselectively formed in all cases when iodo(hetero)aryl substrates were used in the resence of all of the three 3-aminolactams under mild reaction conditions. The products synthesized in the reactions mentioned above were isolated in moderate to high yields.

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