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As a candidate for bifunctional asymmetric catalysts containing a half-sandwich C-N chelating Ir(III) framework (azairidacycle), a dinuclear Ir complex with an axially chiral linkage is newly designed. An expedient synthesis of chiral 2,2'-bis(aminomethyl)-1,1'-binaphthyl ( 1 ) from 1,1-bi-2-naphthol (BINOL) was accomplished by a three-step process involving nickel-catalyzed cyanation and subsequent reduction with Raney-Ni and KBH 4 . The reaction of ( S )- 1 with an equimolar amount of [IrCl 2 Cp*] 2 (Cp* = η 5 -C 5 (CH 3 ) 5 ) in the presence of sodium acetate in acetonitrile at 80 °C gave a diastereomeric mixture of new dinuclear dichloridodiiridium complexes ( 5 ) through the double C-H bond cleavage, as confirmed by 1 H NMR spectroscopy. A loss of the central chirality on the Ir centers of 5 was demonstrated by treatment with KOC(CH 3 ) 3 to generate the corresponding 16e amidoiridium complex 6 . The following hydrogen transfer from 2-propanol to 6 provided diastereomers of hydrido(amine)iridium retaining the bis(azairidacycle) architecture. The dinuclear chlorido(amine)iridium 5 can serve as a catalyst precursor for the asymmetric transfer hydrogenation of acetophenone with a substrate to a catalyst ratio of 200 in the presence of KOC(CH 3 ) 3 in 2-propanol, leading to ( S )-1-phenylethanol with up to an enantiomeric excess (ee) of 67%.

New Bifunctional Bis(azairidacycle) with Axial Chirality via Double Cyclometalation of 2,2′-Bis(aminomethyl)-1,1′-binaphthyl