Co-Catalysis for Hydroamidocarbonylation of Alkynes with Amides over a Bifunctional Ligand-Based Pd Catalyst.

ABSTRACT

The hydroamidocarbonylation of alkynes with amides allows for the synthesis of α,ß-unsaturated imides with the advantage of 100% atomic economy. Herein, the bifunctional ligand (L1) containing a sulfonic acid group (-SO3 H) and phosphino-fragment enable the Pd catalyst to accomplish the hydroamidocarbonylation of alkynes with amides. It was found that, due to an intramolecular synergetic effect, the L1-based Pd-catalyst exhibited much higher activity than the individual mechanical mixtures of Xantphos-based Pd-complex and MeSO3 H. The formation and stability of Pd-H species were promoted by the presence of L1, which was verified by in situ high-pressure FT-IR analysis. Under the optimized conditions, the target products of the branched imides were obtained with yields in the range of 46-87% over the L1-based Pd-catalyst. Advantageously, as an ionic ligand, the L1-based Pd-catalyst could be recycled for 4 runs in the ionic liquid of [Bmim]NTf2 without any obvious activity loss and detectable metal leaching.