Compound 45

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Compound data: NMR

Synthetic procedure: See article for the definitive version of this procedure and for full experimental details.

General Procedure for the Amination Reaction Using Ammonium Salts – GP2: A dry tube equipped with a stirring bar was charged with NCS (1.0 equiv.), Ru(bpy)₃Cl₂ (5 mol%) and the ammonium salt (1.0 equiv.). The tube was capped with a Supelco aluminium crimp seal with septum (PTFE/butyl), evacuated and refilled with N₂ (x 3). The solvent (0.1M) (dry and degassed by bubbling through with N₂ for 20 min) and the N,N-diisopropylehtylamine (1.1 equiv.) were added and the mixture was stirred for 30/60 min in the dark. The arene (2.0 equiv.) and HClO₄ (4.0 equiv.) were added and the blue LEDs were immediately switched on. The mixture was stirred in front of blue LEDs for 2 h (in some cases the mixture was cooled to 0 °C just before blue LEDs irradiation, see below for individual examples). KOH (1 M in brine) and EtOAc were added and the mixture was shaken vigorously. The aqueous layer was extracted with EOAc (x 3), the combined organic layers were dried (MgSO₄), filtered and evaporated. Purification by flash column chromatography on silica gel gave the products. Following GP2 outlined above in 1,1,1,3,3,3-hexafluoro-i-propanol (HFIP), 3-hydroxypiperidine hydrochloride (14 mg, 0.1 mmol) gave 45 (7 mg, 40%) as an oil. R_f 0.19 [petrol–EtOAc (3:1)]; FT-IR ν_max (film)/cm^–1 3353, 2940, 2804, 1597, 1494, 1380, 1332, 1064; ¹H NMR (400 MHz, CDCl₃) δ 7.26 (2H, m), 6.96 (2H, d, J = 8.0 Hz), 6.88 (1H, t, J = 7.2 Hz), 3.97–3.91 (1H, m), 3.30 (1H, br dd, J = 11.7, 3.1 Hz), 3.12–3.06 (3H, m), 2.21 (1H, br s), 1.97–1.78 (2H, m), 1.73–1.59 (2H, m); ¹³C NMR (125 MHz, CDCl₃) δ 152.0, 129.1, 120.2, 117.4, 66.4, 57.6, 50.3, 32.0, 22.0; HRMS (APCI): Found MH⁺ 178.1226, C₁₁H₁₆NO requires 178.1226.