2,3-Bis(diphenylphosphino)butane

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 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. Synthesis of Complexes while the complexes were prepared in accordance with the procedure Synthesis of Complexes

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 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. Synthesis of Complexes while the complexes were prepared in accordance with the procedure Synthesis of Complexes

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:210.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In an autoclave made of metal were placed 2.53 g of meta-chlorotoluene, 35.5 mg of palladium chloride, 426 mg of bisdiphenylphosphinobutane and 3.04 g of potassium carbonate. The air in the autoclave was replaced with carbon monoxide introduced thereinto in several times, after which carbon monoxide was further introduced to adjust its pressure therein to 50 kg/cm2. The reaction was carried out with stirring for 3 hours on a salt bath at a bath temperature of 210° C. After completion of the reaction, the reaction mixture was cooled to room temperature and water was added. The aqueous layer was separated, after which acid was added thereto and the deposited crystals were collected by filtration and dried. Thus, 1.10 g of the desired compound meta-methylbenzoic acid was obtained. introduced After completion of the reaction the reaction mixture was cooled to room temperature The aqueous layer was separated after which acid was added the deposited crystals were collected by filtration dried

Conditions: temp:210.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In an autoclave made of metal were placed 11.2 g of chlorobenzene, 17.5 mg of palladium chloride, 427 mg of bisdiphenylphosphinobutane and 3.1 g of potassium carbonate. The air in the autoclave was replaced with carbon monoxide introduced thereinto in several times, after which carbon monoxide was further introduced to its pressure therein to 50 kg/cm2. The reaction was carried out with stirring for 3 hours on a salt bath at a bath temperature of 210° C. After completion of the reaction, the reaction mixture was cooled to room temperature and water was added. The aqueous layer was separated, after which acid was added thereto and the deposited crystals were collected by introduced After completion of the reaction the reaction mixture was cooled to room temperature The aqueous layer was separated after which acid was added the deposited crystals were collected by

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 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. Synthesis of Complexes while the complexes were prepared in accordance with the procedure Synthesis of Complexes