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Highly stereoselective and oxydative addition of protic molecules to iridium(I) complexes and asymmetric hydrogenation of prochiral imines.

质子分子与铱(I)配合物的高度立体选择性和氧化加成以及前手性亚胺的不对称氢化。

基本信息

批准号：
15550090
负责人：
YAMAGATA Tsuneaki
金额：
$ 2.37万
依托单位：
Osaka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2003
资助国家：
日本
起止时间：
2003 至 2005
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15550090/
关键词：
asymmetric hydrogenation iridium catalyst carboxylato imine optical active amine カルボキシラト

项目摘要

Mononuclear iridium(III) complexes of general formula IrX(H)(O_2CR)[(S)-binap](2, R=CH_3 ; 3,R=Ph ; 4,R=C_6H_4CH_3-p ; a, X=Cl ; b, X=Br ; c, X=I) were prepared by one-pot reaction of [Ir(μ-X)(cod)]_2 with 2 equiv of (S)-BINAP [=2,2'-bis(diphenylphosphino)-1,1'-binaphthyl] and an excess of the corresponding carboxylic acid in toluene. The structure of (S)-2-4 bearing an (S)-BINAP was confirmed to be OC-6-23-A (Λ-conformation) by X-ray analysis of (S)-4a-c. In this reaction, the iridium(I) complex {Ir(μ-Cl)[(S)-binap]}_2 [(S)-5a] and pentacoordinated iridium(I) complexes IrX(cod)[(S)-binap] [(S)-7b, X=Br ; (S)-7c, X=I] were generated prior to the oxidative addition of carboxylic acid. Cationic dinuclear iridium(III) complexes of general formula [{Ir(H)[(S)-binap]}_2(μ-X)_3]X [(S)-8 : a, X=Cl ; b, X=Br ; c, X=I] were prepared, and their cationic bifacial octahedral dinuclear structure was characterized by spectral data and combustion analysis. The anionic portion of these complexes could … More be replaced by NaPF_6, leading to the corresponding PF_6 salts [{Ir(H)[(S)-binap]}_2(μ-X)_3]PF_6 [(S)-8 : d, X=Cl ; e, X=Br ; f, X=I]. Iodo-acetate complexes of p-TolBINAP (=2,2'-bis(di-4-tolylphosphino)-1,1'-binaphthyl) [(S)-9c] and SYNPHOS [=2,2',3,3'-tetrahydro(5,5'-bi-1,4-benzodioxin)-6,6'-diyl]bis(diphenylphosphine)] [(S)-10c] were also prepared according to the method used for the BINAP complex (S)-2c and were characterized spectroscopically. Cationic dinuclear complexes of p-TolBINAP [(S)-11c] and SYNPHOS [(S)-12c] were also generated. Using these complexes, the effect of halide variation was studied by asymmetric hydrogenation of 2-phenylpyrrolidine (13) and 2-phenyl-4,5,6,7-tetrahydro-3H-azepine (15) along with 2-phenylquinoline (16), and the results indicated that iodide complexes were better catalyst precursors for catalytic activity than the corresponding chloride and bromide complexes, but were not superior in enantioselectivity. I have acquired three patents. The titles of patents are as follows, a : Method for preparation of optically active neutral rhodium-phosphine complexes as asymmetric synthesis catalysts. b : Preparation of iridium complexes as catalysts for the synthesis of optically active amines. c : Preparation of optically active phenylamines. Less

通式为IrX（H）（O_2CR）[（S）-binap]的单铱（III）配合物（2，R= CH_3; 3，R=Ph ; 4，R= C_6H_4CH_3-p ; a，X=Cl ; B，X=Br ;[Ir（μ-X）（cod）]_2与2当量的（S）-BINAP [= 2，2 ′-bis]反应，一锅法合成了2个新的配合物（二苯基膦基）-1，1 '-联萘]和过量的相应羧酸的甲苯溶液。通过对（S）-4a-c的X射线分析，证实带有（S）-BINAP的（S）-2-4的结构为OC-6-23-A（Λ-构象）。在此反应中，在羧酸氧化加成之前，生成了铱（I）配合物{Ir（μ-Cl）[（S）-binap]}_2 [（S）-5a]和五配位铱（I）配合物IrX（cod）[（S）-binap] [（S）-7b，X=Br ;（S）-7c，X=I]。合成了通式为[{Ir（H）[（S）-binap]}_2（μ-X）_3]X [（S）-8：a，X=Cl ; B，X=Br ; c，X=I]的阳离子双核铱（III）配合物，通过光谱和燃烧分析表征了其阳离子双面八面体双核结构。这些络合物的阴离子部分可以 ...更多信息用NaPF_6取代，得到相应的PF_6盐[{Ir（H）[（S）-binap]}_2（μ-X）_3]PF_6 [（S）-8：d，X=Cl ; e，X=Br ; f，X=I]。还根据BINAP络合物（S）-2c所用的方法制备p-TolBINAP（= 2，2 '-双（二-4-甲苯基膦基）-1，1'-联萘）[（S）-9c]和SYNPHOS [= 2，2 '，3，3'-四氢（5，5 '-双-1，4-苯并二恶英）-6，6'-二基]双（二苯基膦）] [（S）-10c]的碘-乙酸盐络合物，并通过光谱进行表征。还生成了p-TolBINAP [（S）-11c]和SYNPHOS [（S）-12c]的阳离子双核配合物。以2-苯基吡咯烷（13）和2-苯基-4，5，6，7-四氢-3H-氮杂卓（15）为催化剂，沿着2-苯基喹啉（16）进行不对称氢化反应，研究了卤化物变化对催化活性的影响，结果表明碘配合物是比相应的氯配合物和溴配合物更好的催化剂前体，但对映选择性并不上级。我获得了三项专利。专利名称如下：a.作为不对称合成催化剂的光学活性中性铑-膦配合物的制备方法。B：制备铱络合物作为合成光学活性胺的催化剂。c：光学活性苯胺的制备。少