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

ABSTRACT: 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 KBH₄. The reaction of (S)-1 with an equimolar amount of [IrCl₂Cp*]₂ (Cp* = ?⁵-C₅(CH₃)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 ¹H NMR spectroscopy. A loss of the central chirality on the Ir centers of 5 was demonstrated by treatment with KOC(CH₃)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(CH₃)₃ in 2-propanol, leading to (S)-1-phenylethanol with up to an enantiomeric excess (ee) of 67%.

SUBMITTER: Sato Y 

PROVIDER: S-EPMC7926664 | biostudies-literature | 2021 Feb

REPOSITORIES: biostudies-literature