Arenesulfonamides 10, cyanamide 29, and sulfamide 32 react with allylic bis-carbonates 8 (Z and E) and 9 under Pd(0)-catalysis to afford medium and large unsaturated heterocycles instead of three and/or five-membered ring compounds. Stable 15-membered palladium-containing rings were also isolated from arenesulfonamides and 8, with three trans olefinic systems coordinated to the metal. NMR and MALDI-TOF MS experiments were used for structure elucidations. Suitable hydrogenation conditions to give the saturated macrocycles have been found.
- Acidic N-nucleophiles
- Palladium Catalysis
Cerezo, S., Cortés, J., López-Romero, J. M., Moreno-Mañas, M., Parella, T., Pleixats, R., & Roglans, A. (1998). Palladium(0)-catalyzed allylation of highly acidic and non-nucleophilic arenesulfonamides, sulfamide, and cyanamide. II. Formation of medium and large heterocycles. Tetrahedron, 54(49), 14885-14904. https://doi.org/10.1016/S0040-4020(98)00931-4