{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,2,28]],"date-time":"2026-02-28T04:29:42Z","timestamp":1772252982883,"version":"3.50.1"},"reference-count":50,"publisher":"MDPI AG","issue":"4","license":[{"start":{"date-parts":[[2021,2,22]],"date-time":"2021-02-22T00:00:00Z","timestamp":1613952000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/100008608","name":"Sumitomo Foundation","doi-asserted-by":"publisher","award":["140103"],"award-info":[{"award-number":["140103"]}],"id":[{"id":"10.13039\/100008608","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>As a candidate for bifunctional asymmetric catalysts containing a half-sandwich C\u2013N chelating Ir(III) framework (azairidacycle), a dinuclear Ir complex with an axially chiral linkage is newly designed. An expedient synthesis of chiral 2,2\u2032-bis(aminomethyl)-1,1\u2032-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* = \u03b75\u2013C5(CH3)5) in the presence of sodium acetate in acetonitrile at 80 \u00b0C gave a diastereomeric mixture of new dinuclear dichloridodiiridium complexes (5) through the double C\u2013H 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%.<\/jats:p>","DOI":"10.3390\/molecules26041165","type":"journal-article","created":{"date-parts":[[2021,2,22]],"date-time":"2021-02-22T20:42:51Z","timestamp":1614026571000},"page":"1165","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":4,"title":["New Bifunctional Bis(azairidacycle) with Axial Chirality via Double Cyclometalation of 2,2\u2032-Bis(aminomethyl)-1,1\u2032-binaphthyl"],"prefix":"10.3390","volume":"26","author":[{"given":"Yasuhiro","family":"Sato","sequence":"first","affiliation":[{"name":"Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, 2-12-1-E4-1 O-okayama, Meguro-ku, Tokyo 152-8552, Japan"},{"name":"Hazardous Materials Laboratory, Research and Development Division, National Research Institute of Fire and Disaster, Jindaiji-higashimachi 4-35-3, Chofu, Tokyo 182-8508, Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Yuichi","family":"Kawata","sequence":"additional","affiliation":[{"name":"Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, 2-12-1-E4-1 O-okayama, Meguro-ku, Tokyo 152-8552, Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Shungo","family":"Yasui","sequence":"additional","affiliation":[{"name":"Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, 2-12-1-E4-1 O-okayama, Meguro-ku, Tokyo 152-8552, Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4685-8833","authenticated-orcid":false,"given":"Yoshihito","family":"Kayaki","sequence":"additional","affiliation":[{"name":"Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, 2-12-1-E4-1 O-okayama, Meguro-ku, Tokyo 152-8552, Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Takao","family":"Ikariya","sequence":"additional","affiliation":[{"name":"Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, 2-12-1-E4-1 O-okayama, Meguro-ku, Tokyo 152-8552, Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2021,2,22]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"1300","DOI":"10.1021\/ar700134q","article-title":"Asymmetric transfer hydrogenation of ketones with bifunctional transition metal-based molecular catalysts","volume":"40","author":"Ikariya","year":"2007","journal-title":"Acc. 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