Gold(I) Complexation of Phosphanoxy-Substituted Phosphaalkenes for Activation-Free LAuCl Catalysis

The phosphanoxy-substituted phosphaalkene bearing the P=C-O-P skeleton can be prepared from diphosphene Mes*P=PMes* (Mes*=2,4,6-tBu₃ C₆ H₂ ), and their use for catalysis is of interest. In this paper, complexation of the phosphanoxy-substituted phosphaalkenes with gold are investigated, and the catalytic activity of the mono- and bis(chlorogold) complexes are subsequently evaluated. Reaction of the P=C-O-P compound with (tht)AuCl (tht=tetrahydrothiophene) showed dominant coordination on the sp³ phosphorus, and complete coordination on the sp² phosphorus required removal of tetrahydrothiophene. Atoms In Molecules (AIM) analysis based on the X-ray structure of the mono(chlorogold) complex indicated a pseudo coordinating interaction between the gold center and the P=C unit. The bis(chlorogold) complexes displayed conformational isomerism, and catalyzed the cycloisomerization/alkoxycyclization of 1,6-enyne and for hydration of terminal alkyne without activation treatment. Even the mono(chlorogold) complexes catalyzed the alkoxycyclization reactions without a silver co-catalyst, indicating that the alcohols were effective in activating the AuCl unit.