Polymer-Supported-Cobalt-Catalyzed Regioselective Cyclotrimerization of Aryl Alkynes.

A convoluted poly(4-vinylpyridine) cobalt(II) (P4VP-CoCl) system was developed as a stable and reusable heterogeneous catalyst. The local structure near the Co atom was determined on the basis of experimental data and theoretical calculations. This immobilized cobalt catalyst showed high selectivity and catalytic activity in the [2 + 2 + 2] cyclotrimerization of terminal aryl alkynes. With 0.033 mol % P4VP-CoCl, the regioselective formation of 1,3,5-triarylbenzene was realized without 1,2,4-triarylbenzene formation. Further, a multigram-scale (11 g) reaction proceeded efficiently. In addition, the polymer-supported catalyst was successfully recovered and used three times. X-ray photoelectron spectroscopy analysis of the recovered catalyst suggested that cobalt was in the +2 oxidation state. The 1,3,5-triarylbenzene derivatives were applied to the synthesis of a molecular beam electron resist and a polycyclic aromatic hydrocarbon.