A Bulky Three-Hindered Quadrant Bisphosphine Ligand: Synthesis and Application in Rhodium-Catalyzed Asymmetric Hydrogenation of Functionalized Alkenes.

A bulky three-hindered quadrant bisphosphine ligand, di-1-adamantylphosphino(-butylmethylphosphino)methane, named BulkyP*, has been synthesized via a convergent short pathway with chromatography-free procedures. The ligand is a crystalline solid and can be readily handled in air. Its rhodium(I) complex exhibits very high enantioselectivities and catalytic activities in the asymmetric hydrogenation of functionalized alkenes.

New Approach to the Polymerization of Disubstituted Acetylenes by Bulky Monophosphine-Ligated Palladium Catalysts.

Bulky monophosphine-ligated Pd complexes served as unprecedented admirable catalysts for the polymerization of a disubstituted acetylene. The moderately high polymer yields and cis content of the formed polyacetylene contrasted with those observed for traditional Mo catalyst-based polymer. These Pd catalysts are strong tools to promote the understanding of the structure-property relationships of disubstituted acetylenes.