Copper-Catalyzed Tandem Multi-Component Approach to 1,3-Oxazines at Room Temperature by Cross-Dehydrogenative Coupling Using Methanol as C1 Feedstock

Abstract

A copper(II)-catalyzed multi-component one-pot approach for the synthesis of 1,3-oxazines at room temperature is reported here. Methanol is used as the solvent as well as the carbon source. The methylene carbon of the oxazine product comes from methanol via formaldehyde. tert-Butyl hydroperoxide is used as the oxidant. The reaction uses an environmentally benign metal catalyst and oxidant. No inert atmosphere or precaution is required for the reaction. Most importantly, the reaction avoids the use of carcinogenic formaldehyde.

Key words

methanol - 1,3-oxazine - copper(II) catalyst - multi-component reaction - C–H functionalization

• References

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• 18 Representative Procedure for the Synthesis of 3a 2-Naphthol (1a, 1 mmol, 144 mg), tetrahydroisoquinoline (2a, 1 mmol, 133 mg), and methanol (5 mL) were combined in a round-bottom flask. Cu(OAc)₂ ^. H₂O (10 mol%, 20 mg) and TBHP (70% in H₂O, 2 mmol, 257 mg) were added and the reaction mixture was stirred at r.t. for 15 h. Progress of the reaction was monitored by TLC. Removal of the solvent under vacuum and purification by column chromatography (100–200 mesh silica gel, hexane/ethyl acetate) afforded product 3a as a white solid. Yield: 68% (195 mg). ¹H NMR (300 MHz, CDCl₃): δ = 7.79 (d, J = 7.9 Hz, 1 H), 7.69–7.64 (m, 2 H), 7.53–7.45 (m, 2 H), 7.40–7.30 (m, 3 H), 7.23 (d, J = 7.9 Hz, 1 H), 7.07 (d, J = 8.7 Hz, 1 H), 5.80 (s, 1 H), 4.81 (d, J = 16.3 Hz, 1 H), 4.30 (d, J = 16.6 Hz, 1 H), 3.49–3.41 (m, 1 H), 3.17–3.12 (m, 1 H), 2.97–2.92 (m, 2 H). ¹³C NMR (125 MHz, CDCl₃): δ = 151.7, 134.9, 133.0, 131.5, 129.0, 128.9, 128.8, 128.5, 128.2, 126.5, 126.3, 123.5, 121.2, 118.8, 111.1, 86.9, 51.3, 45.2, 29.2. HRMS (ESI): m/z calcd for C₂₀H₁₇NO [M+H]⁺: 288.1388; found: 288.1389.