Mild, Efficient, One-Pot Synthesis of Imidazolones Promoted by N,O-Bistrimethylsilylacetamide (BSA)

Abstract

The formation of imidazolones by means of dehydrative cyclization was developed, using bistrimethylsilylacetamide. This highly versatile, friendly, safe, and cost-effective reagent exhibited a very large scope of starting materials, since it can promote the formation of 4-benzylidene imidazolones, 4,4-dialkyl-imidazolones, bearing alkyl, aryl, or even no substituent at C2, the latter being unavailable by classical methods. This reagent also afforded clean and high-yielding one-pot reactions in the presence of amine or imine reagents.

Key words

imidazolone - oxazolone - amide dehydration - bistrimethylsilyl acetamide - silylating agent

• References and Notes

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• 21 To a solution of (Z)-4-(4-methoxybenzylidene)-2-phenyloxazol-5(4H)-one (5b, 280 mg, 1 mmol) in pyridine (2 mL) was added methylamine (1 mL of a 1 M solution in THF). The reaction mixture was stirred for 30 min at room temperature, then BSA (407 mg, 2 mmol) was added and the reaction heated to 110 °C overnight. It was cooled, diluted with EtOAc, washed with 1 M citric acid, water and brine, dried over anhydrous Na₂SO₄, filtered, and concentrated under reduced pressure. Purification by flash chromatography using PE and EtOAc provided pure (Z)-4-(4-methoxybenzylidene)-1-methyl-2-phenyl-1H-imidazol-5(4H)-one (7c) as a yellow solid (290 mg, 99%); mp 176 °C. ¹H NMR (300 MHz, DMSO): δ = 8.29 (d, J = 8.9 Hz, 2 H), 7.93 (dd, J = 7.8, 1.7 Hz, 2 H), 7.66–7.55 (m, 3 H), 7.16 (s, 1 H), 7.05 (d, J = 8.9 Hz, 2 H), 3.82 (s, 3 H), 3.27 (s, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 171.80, 161.59, 161.30, 137.26, 134.64, 131.40, 129.55, 129.09, 128.89, 128.70, 127.39, 114.41, 55.46, 29.14. HRMS (CI): m/z calcd for C₁₈H₁₇N₂O₂ [M + H]⁺: 293.1285; found: 293.1290. IR (ATR): 3154, 2947, 1734, 1694, 1574, 1421, 1094 cm^–1. Ideally, these reactions are run in a sealed tube. When carried out in a round-bottomed flask equipped with a reflux condenser, it is necessary to add a further molar equivalent of BSA to achieve completion of the reaction, since some BSA can be lost through evaporation.