<i>N</i>-Phosphino-<i>p</i>-tolylsulfinamide Ligands: Synthesis, Stability, and Application to the Intermolecular Pauson−Khand Reaction

Here we synthesized a family of racemic and optically pure N-phosphino-p-tolylsulfinamide (PNSO) ligands. Their stability and coordination behavior toward dicobalt−alkyne complexes was evaluated. Selectivities of up to 3:1 were achieved in the ligand exchange process with (μ-TMSC2H)Co2(CO)6. The resulting optically pure major complexes were tested in the asymmetric intermolecular Pauson−Khand reaction and yielded up to 94% ee. X-ray studies of the major complex 18a indicated that the presence of an aryl group on the sulfinamide reduces the hemilabile character of the PNSO ligands.