Palladium(II)-catalyzed asymmetric cycloisomerization of enynes with (R)-binap gave axially chiral biaryls with up to 99%ee. The reactivity and enantioselectivity depended on the nature and position of substituent of the arene ring. The enynes with ortho methoxy arene at alkyne terminus gave chiral biaryls with good enantioselectivity.

Gold(I)-catalyzed asymmetric intramolecular cyclization of prochiral 1,3-dihydroxymethyl-2-alkynylbenzene or 1,3-bis(carbamate)-2-alkynylbenzene tricarbonylchromium complexes with axially chiral diphosphine ligand gave planar chiral tricarbonylchromium complexes of 1H-isochromene or 1,2-dihydroisoquinoline with high enantioselectivity. An enantiomeric excess of the planar chiral arene chromium complexes was largely affected by a combination of axially chiral diphosphine(AuCl)2 precatalysts and silver salts. In the case of 1,3-dihydroxymethyl-2-alkynylbenzene chromium complexes, a system of segphos(AuCl)2 with AgBF4 resulted in the formation of the corresponding antipode.

Gold(I)-catalyzed asymmetric cyclization of 1,3-dihydroxymethyl-2-alkynylbenzene chromium complexes gave planar chiral isochromene chromium complexes with high enantioselectivity. Enantiomeric excess of the cyclization products was largely affected by a combination of axially chiral diphosphine(AuCl)2 precatalysts and silver salts. A system of segphos(AuCl)2 with AgBF4 resulted in the formation of the corresponding antipode.

Gold(I)-catalyzed cyclization of o-alkynyl benzaldehyde chromium complexes gave stereoselectively 1-anti- and syn-functionalized 1H-isochromene chromium complexes, respectively, depending on the nature of nucleophiles. Enantiomerically pure trans- and cis-1,3-dimethylisochromans were stereoselectively prepared from a single planar chiral o-(1-propynyl)benzaldehyde chromium complex.Gold(I)-catalyzed cyclization of o-alkynyl benzaldehyde chromium complexes gave stereoselectively 1-anti- and syn-functionalized 1H-isochromene chromium complexes depending on nucleophiles.

The reaction of optically active α,β-unsaturated binuclear Fischer carbene complexes with alkynes gave planar chiral cycloheptatriene chromium complexes via [3+2+2] cycloaddition with high diastereoselectivity.Stereoselective [3+2+2] cycloaddition reaction of optically active binuclear α,β-unsaturated Fischer carbene complexes with alkynes via nickel carbene complexes gave planar chiral cycloheptatriene chromium complexes with high diastereoselectivity. The chromium-coordinated both rings of the product were stereo- and chemoselectively functionalized by utilizing distinct properties of the chromium complex.