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タイトル
和文: 
英文:New Bifunctional Bis(azairidacycle) with Axial Chirality via Double Cyclometalation of 2,2’-Bis(aminomethyl)-1,1’-binaphthyl 
著者
和文: 佐藤 康博, 川田 雄一, 安井 隼吾, 榧木 啓人, 碇屋 隆雄.  
英文: Yasuhiro Sato, Yuichi Kawata, Shungo Yasui, Yoshihito Kayaki, Takao Ikariya.  
言語 English 
掲載誌/書名
和文: 
英文:Molecules 
巻, 号, ページ Vol. 26    No. 4    p. 1165
出版年月 2021年2月22日 
出版者
和文: 
英文:MDPI 
会議名称
和文: 
英文: 
開催地
和文: 
英文: 
公式リンク https://www.mdpi.com/1420-3049/26/4/1165
 
DOI https://doi.org/10.3390/molecules26041165
アブストラクト 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* = η5–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%.

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