反应详情

Synthesis of Complexes using C2 symmetric bis-P ligands (DIOP, BINAP, Cl-MeO-BIPHEP, SEGPHOS, PhanePHOS, DIPAMP, DuPHOS, BDPP, CHIRAPHOS, PPM, PYRPHOS) uses the compound [RuCl2(benzene)], RuCl2(PPh3)3 and trans-RuCl2(NBD)(py)2 as the starting material, while the complexes were prepared in accordance with the procedure published in the literature (Noyori, R.; Takeshi, O.; Hirohito, O. Shohei, H.; Takao, I. J. Am. Chem. Soc. 1995, 117, 2675; Akotsi, O. M.; Meters, K.; Reid, R. D.; McDonald, R.; Bergens, S. H. Chirality 2000, 12, 514-522; BINAP=2,2′-bis(diphenylphosphino)-1,1′-binaphthyl, DIOP=4,5-Bis(diphenylphosphinomethyl)-2,2-dimethyl-1,3-dioxolane, Cl-MeO-BIPHEP=5,5′-Dichloro-6,6′-dimethoxy-2,2′-bis(diphenylphosphino)-1,1′-biphenyl, SEGPHOS=5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole, PhanePHOS=4,12-Bis(diphenylphosphino)-[2.2]-paracyclophane, DIPAMP=1,2-Bis[(2-methoxyphenyl)(phenyl)phosphino]ethane, Me-DuPHOS=1,2-Bis((2S,5S)-2,5-dimethylphospholano)benzene, BDPP=2,4-Bis(diphenylphosphino)pentane, CHIRAPHOS=Bis(diphenylphosphino)butane, PYRPHOS=3,4-bis(diphenylphosphino)-Pyrrolidine, PPM=4-(diphenylphosphino)-2-[(diphenylphosphino)methyl]-Pyrrolidine. Synthesis of Complexes using C1 symmetric bis-P ligand (JosiPHOS, WalPHOS, MandyPHOS) uses the compound RuCl2(PPh3)3 as the starting material which can be obtained easily from hydrated RuCl3 and PPh3 (Steohenson, T. A.; Wilkinson, G. J. Inorg. Nucl. Chem. 1966, 28, 945-956; Josiphos=1-[Diarylphosphano]-2-[1-(dicyclohexylphosphano)ethyl]ferrocene.), while the complexes and RuCl2[(R,S)-Josiphos](PPh3) were prepared in accordance with the procedure published in the literature (Baratta, W.; Ballico, M.; Chelucci, G.; Siega, K.; Rigo, P. Angew. Chem. Int. Ed. 2008, 47, 4362-4365). The monochloride complex (11) was prepared from (10) by reacting with Et3N. The pre-catalysts used for in situ hydrogenation were [RuCl2BINAP(pyridine)2, RuCl2DIOP(pyridine)2, RuCl2(Josiphos)(pyridine)2]. As non-limiting examples of the present invention the synthesis and the characteristics of the complexes (8-25) are described in detail. All the syntheses were carried out under argon atmosphere, using freshly distilled solvents.

1. customSynthesis of Complexes
2. customwhile the complexes were prepared in accordance with the procedure
3. customSynthesis of Complexes