(R)-(+)-N,N-Dimethyl-1-ferrocenylethylamine, A common heterocyclic compound, its traditional synthetic route has been very mature, but the traditional synthetic route has various shortcomings, such as complicated route, low yield, poor purity, etc., below Introduce a new synthetic route.”31886-58-5
To a degassed solution of (R)-1 (829 mg, 3.22 mmol) in THF (4.5 mL) at -78 C was added dropwise sec-BuLi (1.4 M in cyclohexane, 2.5 mL, 3.55 mmol). The resulting deep red solution was stirred for 1 h at -78 C and for 2 h at 0 C. A solution of ZnBr2 (1.3 M in THF, 3.2 mL, 4.19 mmol) was added and the reaction mixture was stirred for further 40 min at 0 C. A degassed solution of [Pd2(dba)3] (148 mg, 0.162 mmol) and tri-(2-furyl)phosphine (tfp) (299 mg, 1.29 mmol) in THF (6 mL) was prepared and stirred for 20 min at r.t. to give a dark green clear solution. To this catalyst solution were transferred a degassed solution of (R,SFc)-1-iodo-2-p-tolylsulfinylferrocene, (R,SFc)-2, (900 mg, 2.00 mmol) in THF (15 mL) and the freshly prepared ferrocenyl-zinc compound. The resulting red-brown solution was heated to reflux under argon at 75 C for 19 h. The reaction mixture was cooled to r.t., quenched with 5 M NaOH (6 mL), diluted with water and extracted with ethyl acetate (3 ¡Á 70 mL). The combined organic phases were washed with water (3 ¡Á 50 mL) and brine (2 ¡Á 50 mL) and dried over MgSO4. The mixture was filtered and the solvent was evaporated. The crude product was purified by column chromatography (silica, PE/EE/NEt3 = 10/10/1 ? 1/2/1). After a second chromatography (aluminium oxide, PE/EE/NEt3 = 1/1/1 ? 1/2/1) was the pure product obtained as an orange solid (yield: 55 mg, 5%). Single crystals suitable for X-ray structure determination were obtained from a solution of the product in EtOAc/PE by slow evaporation of the solvents. M.p.: 158-163 C. 1H NMR (600.1 MHz, CDCl3): delta 1.51 (d, J = 6.9 Hz, 3H, CH3CH), 1.72 (s, 6H, N(CH3)2), 2.42 (s, 3H, Ph-CH3), 3.59 (q, J = 6.9 Hz, 1H, CH3CH), 4.09 (m, 1H, H3?), 4.24 (s, 6H, Cp? + H3), 4.27 (s, 5H, Cp?), 4.39 (dd, J1 = J2 = 2.5 Hz, 1H, H4), 4.42 (dd, J1 = J2 = 2.5 Hz, 1H, H4?), 4.70 (m, 1H, H5?), 4.76 (m, 1H, H5), 7.31 (d, J = 8.0 Hz, 2H, Ph-meta), 7.67 (d, J = 8.0 Hz, 2H, Ph-ortho). 13C{1H} NMR (150.9 MHz, CDCl3): delta 18.9 (bs, CH3CH), 21.5 (Ph-CH3), 40.9 (2C, N(CH3)2), 55.5 (CH3CH), 66.9 (C4), 67.8 (2C, C3 + C3?), 68.8 (C4?), 69.8 (5C, Cp?), 70.7 (5C, Cp?), 71.8 (C5), 73.9 (C5?), 82.0 (C1), 88.6 (C1?/C2?), 89.5 (C2), 93.9 (C1?/C2?), 125.7 (2C, Ph-ortho), 129.4 (2C, Ph-meta), 141.0 (Ph-ipso), 141.4 (Ph para). HR-MS (ESI, MeOH/MeCN): m/z [M + H]+ calcd. 580.1060 for C31H34Fe2NOS; found: 580.1047. [alpha]lambda20 (nm): -739 (589), -843 (578), -1380 (546) (c 0.225, CHCl3).
Chemical properties determine the actual use. Each compound has specific chemical properties and uses. We look forward to more synthetic routes in the future to expand reaction routes of (R)-(+)-N,N-Dimethyl-1-ferrocenylethylamine, 31886-58-5
Reference£º
Article; Gross, Manuela A.; Mereiter, Kurt; Wang, Yaping; Weissensteiner, Walter; Journal of Organometallic Chemistry; vol. 716; (2012); p. 32 – 38;,
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations
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