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

用[Ir(μ-X)(cod)]_2与2等量的(S)-binap[=2,2′-双（二苯基膦）-1,1′-联萘基]和过量的相应羧酸在甲苯中进行一锅反应，制备了通式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）的单核铱（III）配合物。通过对(S)-4a-c的x射线分析，证实(S)-2-4轴承和(S)-BINAP的结构为OC-6-23-A （Λ-conformation）。在该反应中，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]是在羧酸氧化加入前生成的。[{Ir(H)[(S)-binap]}_2(μ-X)_3]X [(S)-8: a， X=Cl的阳离子双核铱（III）配合物b， X=Br；c， X=I]，并通过光谱数据和燃烧分析对其阳离子双八面体双核结构进行了表征。这些配合物的阴离子部分可以更多地被NaPF_6取代，生成相应的PF_6盐[{Ir(H)[(S)-binap]}_2(μ-X)_3]PF_6 [(S)-8: d， X=Cl；e， X=Br；f, X =我]。根据BINAP配合物(S)-2c的制备方法，制备了对tolbinap（=2,2′-双（二-4-苯基膦）-1,1′-联萘基）[(S)-9c]和SYNPHOS[=2,2′，3,3′-四氢（5,5′-双-1,4-苯并二氧辛）-6,6′-二基]双（二苯基膦）][(S)-10c]的碘乙酸配合物，并对其进行了光谱表征。还生成了p-TolBINAP [(S)-11c]和SYNPHOS [(S)-12c]的阳离子双核配合物。利用这些配合物，研究了2-苯基吡咯烷（13）和2-苯基-4,5,6,7-四氢- 3h -氮平（15）与2-苯基喹啉（16）的不对称加氢对卤化物变化的影响，结果表明，碘化物配合物的催化活性比相应的氯和溴配合物更好，但在对映选择性上并不优于相应的氯和溴配合物。我已经获得了三项专利。专利名称如下：a：一种用作不对称合成催化剂的光活性中性膦铑配合物的制备方法。b：制备铱配合物作为合成旋光性胺的催化剂。c：旋光性苯胺的制备。少

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