Palladium-Catalyzed Three-Component Coupling of Propargylic Oxiranes, Phenols and Carbon Dioxide

Abstract

(Z)-1-Phenoxyalkenyl-substituted cyclic carbonates have been produced from three-component coupling of propargylic oxiranes, phenols and carbon dioxide in the presence of palladium catalyst. The scope and limitations of this reaction have been ­examined by using various phenols and propargylic oxiranes. A plausible mechanism for the reaction is also proposed.

Key words

carbon dioxide - cyclic carbonates - epoxides - three-component coupling - palladium

References and Notes

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4

General Procedure for the Palladium-Catalyzed Three-Component Coupling of Alkynylepoxides with Phenol and CO ₂ (Table 1, Entry 12).: To a stirred solution of alkynylepoxide 1a (32.9 mg, 166 µmol) in dioxane, were added p-cresol (20.8 µL, 199 µmol), Pd₂(dba)₃·CHCl₃ (8.6 mg, 8.3 µmol), dppp (13.7 mg, 33.2 µmol) and 3 Å MS (32.9 mg) at r.t., and stirring was continued for 20 h at 50 °C under CO₂ atmosphere. After filtration of the reaction mixture through a Celite pad followed by evaporation of the solvent, the residue was chromatographed on silica gel with hexane-EtOAc (96:4) as eluent to give the cyclic carbonate 3aa (40.9 mg, 70%) as colorless needles; mp 84-86 °C (from hexane-EtOAc). IR (neat): 2947, 1807, 1504 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 7.38 (d, J = 1.7 Hz, 2 H), 7.18-7.26 (m, 3 H), 6.97 (d, J = 8.8 Hz, 2 H), 6.81 (d, J = 8.8 Hz, 2 H), 6.58 (s, 1 H), 4.85 (dd, J = 5.1, 5.4 Hz, 1 H), 2.22 (s, 3 H), 2.13-2.19 (m, 1 H), 1.83-2.03 (m, 3 H), 1.60-1.66 (m, 3 H), 1.43-1.47 (m, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 154.3, 153.1, 147.3, 132.7, 131.8, 130.2, 129.3, 128.3, 128.0, 117.3, 114.8, 84.1, 77.7, 30.2, 26.3, 20.4, 18.8, 17.7. MS: m/z = 350 [M⁺]. Anal. Calcd for C₂₂H₂₂O₄: C, 75.41; H, 6.35. Found: C, 75.35; H, 6.33.

5

Spectroscopic Data for 4a: colorless oil. IR (neat): 2947, 1809, 1491 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 7.32-7.47 (m, 5 H), 4.75 (dd, J = 5.12, 5.12 Hz, 1 H), 2.30-2.36 (m, 1 H), 2.11-2.18 (m, 1 H), 1.87-2.01 (m, 2 H), 1.72-1.78 (m, 1 H), 1.47-1.65 (m, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 153.8, 131.9, 129.4, 128.4, 120.9, 88.3, 84.1, 80.2, 78.0, 34.2, 25.4, 20.0, 18.5. MS: m/z = 242 [M⁺]. HRMS: m/z [M⁺] calcd for C₁₅H₁₄O₃: 242.0943; found: 242.0952.

7

In these reactions, trace amount of the corresponding (Z)-phenoxyalkenyl-substituted oxiranes (see ref. 3b) were obtained as byproducts.