Pillar[5]arenes, as a new intriguing class of calixarene analogues, were functionalized with ten diglycolamide (DGA) arms on both sides (rims) of the pillar framework and evaluated for their extraction behaviour towards Am(III) and Eu(III). These novel extractants exhibit excellent separation and extraction efficiency, suggesting its significant potential for nuclear waste remediation. Laser induced fluorescence experiments disclosed strong complexation of the trivalent metal ions with the pillararene-DGA ligands.

Reaction of potassium aryloxymethyltrifluoroborates 1 with α,β-unsaturated carbonyl compounds 2 in the presence of a chiral diene-rhodium catalyst in HO at 100 °C introduced 2-methoxyaryl groups at the β-position of 2 with high enantioselectivity in high yields. The reaction is assumed to proceed through 1,4-Rh shift from aryloxymethyl-Rh intermediate to 2-methoxyaryl-Rh. The high availability of phenol derivatives makes this asymmetric conjugate arylation synthetically useful.

The addition of arylzinc reagents ArZnCl 1 to alkynes 2 was found to be catalyzed by rhodium complexes in the presence of a catalytic amount of zinc chloride. The selectivity in giving 2-arylalkenylzinc species 3 or ortho-alkenylarylzinc species 4, the latter of which is generated through 1,4-Rh migration from alkenyl to aryl in the catalytic cycle, is controlled by the ligands on rhodium. Ligands cod and binap gave 3 and 4, respectively, with high selectivity.

A series of novel chiral diene ligands (1R,4S)-L 1 , which are based on the bicyclo[2.2.1]­heptadiene skeleton and are substituted with methyl and an ester group at the bridgehead carbons, were synthesized through rhodium-catalyzed asymmetric arylative bis-cyclization of 1,6-enyne 1 as a key step. The rhodium catalyst with one of the (1R,4S)-L 1 ligands was used for the asymmetric bis-cyclization of 1 giving bicyclic product (1S,4R)-2 of 99% ee, which is a synthetic precursor of (1S,4R)-L 1 ligands.

The desymmetric arylation of prochiral cyclohexadienones with ArZnCl in the presence of an (R)-segphos–rhodium catalyst gave high yields of the corresponding cyclohexenones, which contain a chiral arylated carbon center at the β-position and a chiral all-carbon quaternary center at the γ-position, with high diastereo- and enantioselectivities. This catalytic system was also applied to the arylation of spirocarbocyclic cyclohexadienones and afforded the corresponding cyclohexenones bearing a chiral spiro quaternary carbon with high dr and ee.