A gold(I) complex with a 1,1′-binaphthyl-substituted diphosphene was synthesized and fully characterized. A phosphorus atom with a less-hindered binaphthyl group coordinates to a gold(I) moiety in an η 1 fashion. Both experiment and theoretical calculations supported the facile rotation around the C(Naph)−P bond in neutral and cationic diphosphene− gold(I) complexes. The newly obtained complex 2 was applied to the intramolecular hydroarylation of aryl propynyl ethers 5, and 2H-chromenes 6 were formed in 83−94% yield. Furthermore, the chiral diphosphene−gold(I) complex (S)-2 was used in the atropselective reaction to furnish 6b,c with up to 9% ee, which is the first example of the use of a diphosphene as a ligand for the transition-metal-catalyzed organic transformation.
1,1'-Binaphthyl-substituted diphosphene 1 possessing a P[double bond, length as m-dash]P double bond and an axially chiral 1,1'-binaphthyl group was synthesized and fully characterized. Diphosphene 1 was prepared as an optically active form and thus is the first example of a chiral diphosphene. The CD spectra of 1 showed apparent circular dichroism in the longer wavelength region, caused by the P[double bond, length as m-dash]P moiety.
Organophosphorus compounds possessing the P−P double-bond character are intriguing materials in coordination chemistry because it is possible to form a variety of coordination modes from the π-bond in addition to...
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.