Iridium/chiral diene-catalyzed asymmetric 1,6-addition of arylboroxines to alpha,beta,gamma,delta-unsaturated carbonyl compounds.

Iridium-catalyzed asymmetric 1,6-addition of arylboroxines to alpha,beta,gamma,delta-unsaturated carbonyl compounds to give delta-arylated carbonyl compounds in high yields with 90-99% enantioselectivity was realized by use of an iridium/chiral diene complex.

Rhodium-catalyzed aryl- and alkylation-oligomerization of alkynoates with organoboron reagents giving salicylates.

The reaction of alkynoates with aryl- or alkylboron reagents in the presence of a rhodium/diene catalyst gave high yields of salicylate derivatives with high selectivity, which consist of three or four molecules of the alkynoate and one organic group derived from the organoboron reagents.

Rhodium-catalyzed asymmetric hydroarylation of diphenylphosphinylallenes with arylboronic acids.

Rhodium-catalyzed asymmetric hydroarylation of diphenylphosphinylallenes with arylboronic acids proceeded in high yields with high regio- and enantioselectivity to give chiral allylphosphine oxides of up to 98% ee. The structural determination of the key intermediate, a pi-allylrhodium complex, was successful to establish the catalytic cycle of the reaction.

Asymmetric addition of dimethylzinc to N-tosylarylimines catalyzed by a rhodium-diene complex toward the synthesis of chiral 1-arylethylamines.

A rhodium complex coordinated with a chiral diene, (R,R)-2,5-diphenylbicyclo[2.2.2]octa-2,5-diene (Ph-bod), catalyzed the asymmetric addition of dimethylzinc to N-tosylarylimines to give high yields of chiral 1-aryl-1-ethylamines with high enantioselectivity (94-98% ee).

Kinetic studies prove high catalytic activity of a diene-rhodium complex in 1,4-addition of phenylboronic acid to alpha,beta-unsaturated ketones.

In the 1,4-addition of phenylboronic acid to alpha,beta-unsaturated ketones, [Rh(OH)(cod)]2 has a much higher catalytic activity than [Rh(OH)(binap)]2 (cod = 1,5-cyclooctadiene, binap = 2,2'-bis(diphenylphosphanyl)-1,1'-binaphthyl). Kinetic studies revealed that the rate-determining transmetalation step in the catalytic cycle has a large rate constant when [Rh(OH)(cod)]2 is used.