As formed in situ by stirring a mixture with the ligand and metal precursor inside a degassed solvent (two.5 mL) for 30 min at area temperature The catalyst and thedx.doi.org/10.1021/om401074a | Organometallics 2014, 33, 1945-Organometallicssubstrate options had been transferred by way of a stainless steel capillary into either a glass or perhaps a steel autoclave. The argon gas was then replaced by hydrogen gas (3-5 cycles) as well as the pressure was set. Immediately after completion with the reaction, the reaction mixture was filtered by means of a plug of silica. Conversions and ee values with the solution had been determined by either gas chromatography or HPLC. In an work to make sure consistency and reproducibility, all hydrogenations have been carried out at least twice. The following reaction circumstances and methods were applied. MAC: MAC (219.two mg, 1 mmol); [Rh(NBD)2][BF4] + 1.1 equiv of ligand; S/C = 25; solvent MeOH (five mL); p(H2) 1 bar; 20 ; reaction time 16 h. Analysis information for MAC: GC, column PERMABOND-L-Chirasil-Val (25 m); 160 isothermal; MAC 11.1 min, R 25.4 min, S 28.six min. MAA: MAA (143.1 mg, 1 mmol); [Rh(NBD)2][BF4] + 1.1 equiv of ligand; S/C = 25; solvent MeOH (five mL); p(H2) 1 bar; 20 ; reaction time 16 h. Analysis information for MAA: GC, column PERMABONDL-Chirasil-Val (25 m); 110 isothermal; MAA five.three min, R eight.8 min, S ten.9 min. DMI: DMI (158.two mg, 1 mmol); [Rh(NBD)2][BF4] + 1.1 equiv of ligand; S/C = 25; solvent MeOH (5 mL); p(H2) 1 bar; 20 ; reaction time 16 h. Analysis data for DMI: GC, column LIPODEX-E (50 m); 85 isothermal; DMI 46.Formula of 4-Bromo-3-methylpyridin–2-amine two min, S 29.1314538-55-0 Formula 5 min, R 30.7 min. MCA: MCA (162.2 mg, 1 mmol); [Rh(NBD)2][BF4] + 1.1 equiv of ligand; S/C = 25; solvent MeOH (5 mL); p(H2) 20 bar; 20 ; reaction time 20 h. Workup for MCA: after removal of the solvent below lowered stress, the crude solution was dissolved in DCM and extracted with NaOH (two M). The organic phase was discarded. The aqueous phase was created acidic by addition of aqueous HCl (to pH 1) and was extracted twice with DCM (2 ?25 mL). The combined organic phases had been washed with brine and dried more than MgSO4, along with the solvent was removed under lowered pressure. Subsequently, the residue was transformed in to the corresponding methyl ester. The residue was dissolved in MeOH, and diazomethane in Et2O was added till the remedy turned pale yellow and remained this color. Right after the mixture was stirred for 20 min at room temperature, the solvent was removed very carefully beneath lowered pressure as well as the residue was filtered via a quick plug of silica, which had been wetted with MeOH.PMID:23991096 Analysis data for MCA: HPLC, column Daicel, Chiraldex OB-H; temperature 25 ; eluent hexane/iPrOH 97:3; flow rate 0.5 mL/min; detector DAD; Sig 230 nm; substrate 15.eight min, R 10.7 min, S = 11.six min. PCA: PCA (224.two mg, 1 mmol); [Rh(NBD)2][BF4] + 1.1 equiv of ligand; S/C = 100; solvent MeOH (five mL); p(H2) 50 bar; 20 ; reaction time 19 h; esterification to the methyl ester see MCA. Analysis data for MCA: HPLC, column Daicel, Chiraldex OD-H; temperature 25 , eluent hexane/iPrOH 97:three, flow rate 0.5 mL/min; detector DAD; Sig 230 nm; substrate 20 min, R 18 min, S 18.7 min. IPCA-D: IPCA-D (308.four mg, 1 mmol); [Rh(NBD)2][BF4] + 1.1 equiv of ligand; S/C = 25; solvent MeOH (5 mL); p(H2) 50 bar; 20 ; reaction time 20 h. Evaluation data for IPCA-D: HPLC, column Chiralpak IC; temperature 25 ; solvent heptane/EtOH/TFA = 90/10/0.1; flow rate 1.0 mL/min; detector DAD; Sig 230 nm; IPCA-D five.6 min, S eight.7 min, R ten.three min. ACA: ACA (253.three mg, 2.53 mmol); [RuI2(p-cymene)]2 +.
