As conceptually new chiral ligands,we have been developing enantiomerically pure C2-symmetric chiral dienes,whose basic diene skeleton is bicyclo[2.2.1]hepta-2,5-diene (nbd) or bicyclo[2.2.2]octa-2,5-diene (bod).The chiral diene ligands were found to be better than the conventional chiral ligands represented by chiral bisphosphines in terms of both catalytic activity and enantioselectivity in some of the catalytic asymmetric reactions.Their high performance was observed in rhodium-catalyzed asymmetric addition of organoboron reagents to α,β-unsaturated ketones,N-sulfonylimines,and so on.1 Recently,we have developed two new chiral diene ligands: One is (R)-diene* readily obtained through[4+2]cycloaddition of (R)-α-phellandrene with 2-naphthyl acetylenecarboxylate.The other is that based on tetrafluorobenzobarrelene (tfb) skeleton.In this symposium,some of recent advances in chiral diene/Rh-catalyzed asymmetric reactions[2,3]will be presented,which include 1) Asymmetric Arylation of Allyl Sulfones under the Conditions of Isomerization into Alkenyl Sulfones,2) Asymmetric Synthesis of Triarylmethanes by Enantioselective Arylation of Diarylmethylamines,3) Asymmetric Conjugate Alkynylation of Cyclic α,β-Unsaturated Carbonyl Compounds,and 4) Asymmetric Arylation/Defluorination of l-(Trifluoromethyl)alkenes Forming Chiral 1,1-Difluoroalkenes.