(C5), 82.6 (Cq), 82.7 (Cq), 85.7 (Cq), 88.7 (C2); HR-MS (ESI, MeOH/MeCN) m/z [M + H]+ calcd 520.0026 for C24H27BrFe2N, identified 520.0022; []20 (nm) -950?(589), -1062?(578), -1631?(546) (c 0.283, CHCl3). (R,Sp,Sp)-2-[1-(N,N-Dimethylamino)ethyl]-2-diphenylphosphino-1,1-biferrocene ((R,Sp,Sp)-6). To a degassed answer of (R,Sp,Sp)-5 (two.43 g, four.67 mmol) in THF (30 mL) was added dropwise at -40 a solution of sec-BuLi (1.three M in cyclohexane, 4.3 mL, 5.6 mmol). The resulting dark red mixture was stirred for 40 min at -40 and warmed to room temperature, and subsequently chlorodiphenylphosphine (1.1 mL, 6.4 mmol) was added. The mixture was stirred for 18 h at room temperature and for 1 h at 35 . The reaction was quenched at space temperature with 5 mL of saturated aqueous NaHCO3, the solution was extracted twice with ethyl acetate, plus the combined organic phases were washed with water and brine. Soon after drying over MgSO4, filtration, and evaporation with the solvents, the crude product was obtained as an orange solid. Soon after chromatography (aluminum oxide, PE/EE/NEt3 = 100/1/3) the pure solution was obtained as an orange foam (yield: 1.69 g, two.70 mmol, 58 ). Single crystals suitable for X-ray structure determination had been grown from ethyl acetate by slow evaporation of your solvent. Mp: 196- 201 . 1H NMR (500.1 MHz, CDCl3): 1.34 (d, J = six.six Hz, 3H, CH3CH), two.19 (s, 6H, N(CH3)2), three.69 (s, 5H, Cp), three.80 (s, 5H, Cp), 3.88 (q, J = 6.six Hz, 1H, CH3CH), 3.92 (bs, 1H, H3), four.18-4.21 (m, 2H, H3 + H4), four.39 (dd, J1 = J2 = 2.5 Hz, 1H, H4), 5.34-5.36 (m, 1H, H5), 5.39-5.42 (m, 1H, H5), 7.26-7.30 (m, 1H,dx.doi.org/10.1021/om401074a | Organometallics 2014, 33, 1945-OrganometallicsPhB-para), 7.31-7.36 (m, 2H, PhB-meta), 7.36-7.40 (m, 3H, PhA-meta + PhA-para), 7.45-7.49 (m, 2H, PhB-ortho), 7.59-7.63 (m, 2H, PhAortho); PhA pointing toward Cp. 13C1H NMR (125.six MHz, CDCl3): 10.2 (CH3CH), 39.9 (2C, N(CH3)2), 56.6 (CH3CH), 65.7 (C3/C4), 66.Price of 130473-38-0 4 (C3/C4), 67.five (5C, Cp), 69.7 (C4), 70.3-70.7 (6C, Cp + C5), 72.8 (bs, C5), 73.0-73.3 (2C, C3 + C1), 83.eight (C1), 88.0 (C2), 89.6 (d, J = 22.6 Hz, C2), 127.9 (d, J = 7.5 Hz, 2C, PhAmeta), 128.2 (bs, 3C, PhB-meta + PhB-para), 128.8 (PhA-para), 133.1 (d, J = 19.3 Hz, 2C, PhB-ortho), 135.four (d, J = 22.0 Hz, 2C, PhA-ortho), 139.0 (d, J = 11.three Hz, PhA-ipso), 140.2 (d, J = 11.3 Hz, PhB-ipso). 31 1 P H NMR (162 MHz, CDCl3): -20.0. HR-MS (ESI, MeOH/ MeCN): m/z [M + H]+ calcd 626.1362 for C36H37Fe2NP, discovered 626.1351; []23 (nm): -554 (589) (c 0.232, CHCl3). (R,Sp,Sp)-2-[1-(N,N-Dimethylamino)ethyl]-2-diphenylphosphinyl-1,1-biferrocene ((R,Sp,Sp)-7). Approach A: From (R,Sp,Sp)-6 with H2O2. To a option of (R,Sp,Sp)-6 (649 mg, 1.04 mmol) in acetone (150 mL) was added an aqueous solution of H2O2 (30 , 5 mL).634926-63-9 Formula The reaction mixture was stirred for 50 min at area temperature and was then quenched with saturated aqueous Na2S2O3.PMID:28038441 The organic material was extracted with EtOAc, the combined organic phases had been washed with water and brine, dried more than MgSO4 and filtered, as well as the solvents have been evaporated. The crude item was purified by chromatography (aluminum oxide, PE/EA/TEA = 5/1/1), and the pure solution was obtained as a red-orange strong (yield: 608 mg, 0.948 mmol, 91 ). System B: From (R,Sp,Sp)-5 with ClP(O)Ph2. Synthesis process as described for (R,Sp,Sp)-6: (R,Sp,Sp)-5 (1.220 g, two.346 mmol) in THF (26 mL), n-BuLi (1.6 M in hexane, 1.76 mL, 2.815 mmol), and diphenylphosphinyl chloride (0.6 mL, three.167 mmol). Purification by column chromatography (a.