29.six (d, J = 29.9 Hz, CH3CH), 65.9 (C4), 66.4 (d, J = 15.4 Hz, C1), 68.2 (bs, C5), 70.0 (d, J = 6.eight Hz, C4), 70.2 (5C, Cp), 70.5 (5C, Cp), 72.4 (C3), 72.9 (d, J = 4.3 Hz, C3), 74.7 (d, J = 7.eight Hz, C5), 78.9 (d, J = three.9 Hz, C1), 89.six (d, J = 13.4 Hz, C2), 91.four (d, J = two.two Hz, C2), 128.1-129.1 (8C, Ph-meta), 130.3-131.4 (4C, Ph-para), 132.9 (d, J = 9.two Hz, 2C, Ph-ortho), 133.8-134.two (6C, Ph-ortho), 128.5, 130.0, 130.five, 131.8, 132.four (Ph-ipso). 31P1H NMR (162 MHz, CDCl3): 17.four (bs, Fc-PPh2), 29.four (bs, CH3CH-PPh2). HR-MS (ESI, MeOH/MeCN): m/z [M + Na]+ calcd 817.1857 for C46H40Fe2P2Na, discovered 817.1833; []20 (nm): +371?(589) (c 0.265, CHCl3).Post(R,Sp,Sp)- and (R,Sp,Rp)-2-Bromo-2-[1-(N,N-dimethylamino)ethyl]-1,1-biferrocene ((R,Sp,Sp)-5 and (R,Sp,Rp)-5). To a degassed answer of (R)-3 (584 mg, 2.27 mmol) in THF (three mL) was added dropwise at -78 sec-BuLi (1.4 M in cyclohexane, 1.8 mL, 2.52 mmol). The resulting deep red answer was stirred for 1 h at -78 and for 2 h at 0 . A option of ZnBr2 in THF (1.three M, two.3 mL, two.99 mmol) was added, and the reaction mixture was stirred to get a further 40 min at 0 . A answer of [Pd2(dba)3] HCl3 (118 mg, 0.114 mmol) and tris(2-furyl)phosphine (212 mg, 0.913 mmol) in THF was ready. The mixture was degassed and stirred for 20 min at space temperature to offer a dark green clear answer. To this catalyst solution have been transferred a degassed solution of rac-4 (577 mg, 1.476 mmol) in THF (two mL) and also the freshly ready ferrocenylzinc compound. The resulting option was heated under argon at 75 for 19 h. The reaction mixture was cooled to room temperature, quenched with five M NaOH (five mL), diluted with water, and extracted with Et2O (three ?70 mL). The combined organic phases were washed with water (3 ?50 mL) and brine (two ?50 mL) and dried more than MgSO4. The mixture was filtered, the solvents had been evaporated, and also the crude solutions were separated by column chromatography on aluminum oxide. PE eluted excess tfp and PE/Et2O/NEt3 60/1/3 eluted the very first diastereomer (R,Sp,Sp)-5 and excess three, while PE/Et2O/ NEt3 5/5/1 gave the second diastereomer (R,Sp,Rp)-3. Diastereomer (R,Sp,Sp)-5: yield 32 (249 mg, 0.749 mmol). Derivative (R,Sp,Rp)-5: yield 45 (344 mg, 0.661 mmol). (R,Sp,Sp)-5: mp 113-115 ; 1H NMR (500.Amino-PEG3-C2-Amine Chemscene 1 MHz, CDCl3) 1.1338257-80-9 Data Sheet 39 (d, 3H, J = 6.PMID:24456950 7 Hz, CH3CH), two.09 (s, 6H, N(CH3)two), three.78 (q, J = six.7 Hz, 1H, CH3CH), 4.09 (s, 5H, Cp), 4.10-4.12 (bs, 6H, Cp + H4), four.21-4.22 (m, 1H, H3), 4.26 (dd, J1 = J2 = 2.six Hz, 1H, H4), four.49-4.51 (m, 1H, H3), 4.87-4.89 (dd, J1 = 1.five Hz, J2 = 2.five Hz, 1H, H5), five.01-5.03 (m, 1H, H5); 13 C1H NMR (125.8 MHz, CDCl3) 11.5 (CH3CH), 39.8 (2C, N(CH3)two), 56.0 (CH3CH), 66.3 (C4), 66.five (C4), 67.0 (C3), 69.1 (C5), 69.5 (C5), 70.two (5C, Cp), 71.6 (C3), 71.eight (5C, Cp), 79.0 (Cq), 82.3 (Cq), 82.six (Cq), 88.8 (Cq); HR-MS (ESI, MeOH/MeCN) m/z [M + H]+ calcd 520.0026 for C24H27BrFe2N, identified 520.0027; []23 (nm): -850 (589) (c 0.725, CHCl3). (R,Sp,Rp)-5: Mp: 89- 94 ; 1H NMR (400 MHz, CDCl3): 1.51 (d, J = six.9 Hz, 3H, CH3CH), 1.70 (s, 6H, N(CH3)two), 3.42 (q, J = 6.9 Hz, 1H, CH3CH), 4.18 (dd, J1 = 1.four Hz, J2 = 2.five Hz, 1H, H3), four.26 (dd, J1 = J2 = two.six Hz, 1H, H4), four.28 (s, 5H, Cp), four.36 (bs, 6H, Cp + H4), 4.39 (dd, J1 = 1.5 Hz, J2 = two.six Hz, 1H, H5), four.45 (dd, J1 = 1.5 Hz, J2 = 2.6 Hz, 1H, H3), 4.60 (dd, J1 = 1.four Hz, J2 = 2.5 Hz, 1H, H5); 13C1H NMR (100.6 MHz, CDCl3): 20.1 (CH3CH), 41.1 (2C, N(CH3)two), 55.3 (CH3CH), 66.1 (C4), 66.five (C4), 67.0 (C3), 69.six (5C, Cp), 69.8 (C3), 70.1 (C5), 71.five (5C, Cp), 71.6.