Catalyst-Free Process for the Synthesis of 5-Aryl-2-Oxazolidinones via Cycloaddition Reaction of Aziridines and Carbon Dioxide

Abstract

A simple approach for facile synthesis of 5-aryl-2-­oxazolidinones in excellent regioselectivity from aziridines under compressed CO₂ conditions was developed in the absence of any catalyst and organic solvent. The reaction outcome was found to be tuned by subtly adjusting CO₂ pressure. The adduct formed in situ of aziridine and CO₂ is assumed to act as a catalyst in this reaction, which was also studied by means of in situ FT-IR technique.

carbon dioxide - aziridine - catalyst-free - 5-aryl-2-­oxazolidinones

Reference and Notes

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Typical Procedure for the Carboxylation of Aziridine with CO ₂
In a typical reaction, the carboxylation of aziridine with CO₂ was carried out in a 25 mL stainless steel autoclave. Aziridine (1 mmol) was charged into the reactor at r.t. CO₂ was introduced into the autoclave, and then the mixture was stirred at predetermined temperature for 20 min to reach the equilibration. The pressure was then adjusted to the desired pressure, and the mixture was stirred continuously. When the reaction finished, the reactor was cooled in ice-water and CO₂ was ejected slowly. An aliquot of sample was taken from the resultant mixture and dissolved in dry CH₂Cl₂ for GC analysis. GC analyses were performed on Shimadzu GC-2014, equipped with a capillary column (RTX-5, 30 m × 0.25 mm × 0.25 µm) using a flame-ionization detector. The residue was purified by column chromatography on silica gel (eluting with 8:1 to 1:1 PE-EtOAc) to furnish the product. The products were further identified by ^¹H NMR, ^¹³C NMR, and MS which are consistent with those reported in the literature^³a-j and in good agreement with the assigned structures.

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Spectral characteristics for representative examples of the products were provided. 3-Ethyl-5-phenyl-2-oxazolidinone (2a)
Colorless liquid. ^¹H NMR (300 MHz, CDCl₃): δ = 1.17 (t, 3 H, J = 7.2 Hz), 3.29-3.45 (m, 3 H), 3.92 (t, 1 H, J = 8.7 Hz), 5.48 (t, 1 H, J = 7.8 Hz), 7.34-7.42 (m, 5 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 12.4, 38.8, 51.5, 74.2, 125.4, 128.6, 128.8, 138.8, 157.5. ESI-MS: m/z calcd for C₁₁H₁₃NO₂: 191.09; found: 192.29 [M + H]⁺, 214.38 [M + Na]⁺, 405.01 [2 M + Na]⁺.
3-Ethyl-4-phenyl-2-oxazolidinone (3a)
Colorless liquid. ^¹H NMR (300 MHz, CDCl₃): δ = 1.05 (t, 3 H, J = 5.4 Hz), 2.79-2.88 (m, 1 H), 3.48-3.57 (m, 1 H), 4.10 (t, 1 H, J = 6.0 Hz), 4.62 (t, 1 H, J = 6.6 Hz), 4.81 (t, 1 H, J = 5.4 Hz),7.30-7.44 (m, 5 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 12.1, 36.9, 59.4, 69.8, 127.0, 129.0, 129.2, 137.9, 158.1. ESI-MS: m/z calcd for C₁₁H₁₃NO₂: 191.09; found: 192.29 [M + H]⁺, 214.38 [M + Na]⁺.

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CO₂ activation by tertiary amines:

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