Nickel-Catalyzed Allylation of α-Amido Sulfones To Form Protected Homoallylic Amines

Abstract

The allylation of stable, protected imine precursors, α-amido sulfones, with allylic acetates to form homoallylic amines is catalyzed by nickel under mild reducing conditions. Aliphatic and aryl imines are tolerated, as are substituted allylic acetates. In the case of substituted allylic acetates, high diastereoselectivity and regioselectivity is observed in some cases and the branched product is obtained almost exclusively.

Key words

nickel - allylation - amines - imines - reduction

• References and Notes

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• 24 Typical Procedure for the Allylation of α-Amido SulfonesOn the benchtop, an oven-dried 1-dram vial equipped with a Teflon-coated stir bar was charged with 4,4′-di-tert-butyl-2,2′-bipyridine (2.7 mg, 0.0100 mmol), NiCl₂(dme) (2.0 mg, 0.0100 mmol), tert-butyl cyclohexyl(phenylsulfonyl)methylcarbamate (177 mg, 0.500 mmol, 1.00 equiv), N,N-dimethylacetamide (DMA) (1.00 mL), a solution of cinnamyl acetate (91.8 μL, 0.550 mmol, 1.10 equiv in 1.00 mL DMA), Et₃N (1.40 μL, 0.0100 mmol), dodecane (10.0 μL), and Mn⁰ (54.9 mg, 1.00 mmol). The reaction vial was then capped with a screw cap fitted with a PTFE-faced silicone septum and stirred (1200 rpm) at 40 °C. After 19 h, the reaction mixture was then filtered through a short silica pad (1.5 cm wide × 2 cm high), and the pad was washed with Et₂O (75 mL) before the filtrate was concentrated in vacuo. The residue was then purified by flash chromatography (hexanes–acetone, 95:5) to afford the pure homoallylic amine (Table 2, entry 5) as a white solid (124 mg, 75% yield). X-ray crystallography confirmed that the syn isomer was obtained; mp 101–103 °C. Due to the existence of rotamers at ambient temperature, the ¹H NMR spectrum was obtained at 55 °C: ¹H NMR (400 MHz, CDCl₃, 55 °C): δ = 7.28–7.15 (m, 5 H), 6.03 (dt, J = 17.1, 8.8 Hz, 1 H), 5.09–5.05 (m, 2 H), 4.06 (br s, 1 H), 3.86 (br s, 1 H), 3.43 (t, J = 8.2 Hz, 1 H), 1.29 (s, 9 H), 1.75–0.86 (series of m, 11 H). ¹³C NMR (126 MHz, CDCl₃): δ = 155.9, 141.6, 139.8, 128.5, 128.4, 126.5, 115.9, 78.8, 57.7, 52.9, 39.4, 31.2, 28.4, 28.3, 26.5, 26.4, 26.3. IR: 3341, 2924, 1678, 1535, 1173 cm^–1. LRMS (ESI⁺): m/z = 352.3 [M + Na⁺]. HRMS (ESI⁺): m/z [M + H⁺] calcd for C₂₁H₃₂NO₂: 330.243; found: 330.244. X-ray quality crystals were grown by slow evaporation of acetone.