Carbonylation with CO₂ and Phosphorus Electrophiles: A Convenient Method for the Synthesis of 2-Oxazolidinones from 1,2-Amino Alcohols

Abstract

2-Oxazolidinones were prepared in good yields from 1,2-amino alcohols and CO₂ in the presence of tetramethyl­phenylguanidine (PhTMG) as a base and a variety of phosphorus electrophiles under mild conditions. This procedure is advantageous over previous methodologies and relies on a novel carbonylation procedure that utilizes nontoxic CO₂ and phosphorus electrophiles.

Oxazolidinones - 1,2-amino alcohols - carbonylation - guanidines.

References and Notes

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17

Purchased from Aldrich chemical company.

18

Representative Procedure for the Synthesis of 2-Oxazolidinones 4a-j
A solution of (1S,2R)-norephedrine (3a, 210 mg, 1.39 mmol) and tetramethylphenylguanidine (290 mg, 1.52 mmol, 110 mol%) in anhyd MeCN (10 mL) was cooled to -40 ˚C with a dry ice-acetone bath. Carbon dioxide was slowly bubbled through the solution for 5 min, and then diphenylphosphoryl azide (DPPA) (0.30 mL, 1.39 mmol, 100 mol%) was added dropwise. Carbon dioxide bubbling was maintained for a further 15 min, and the reaction mixture was stirred overnight while it was slowly allowed to reach 20 ˚C. The resulting solution was concentrated almost to dryness. The residue was dissolved in CHCl₃ (30 mL) and washed with a 10% Na₂CO₃ (previously saturated with NaCl) solution (1×). The aqueous layer was extracted with CHCl₃. The combined organic layers were washed with 1 M HCl (previously saturated with NaCl) solution (1×). The aqueous layer was further extracted with CHCl₃. The combined organic layers were dried over Na₂SO₄ and solvents removed under reduced pressure. The residue was purified by flash chromatography on SiO₂ (hexanes-EtOAc, 4:1 to 2:1) to afford 185 mg of (4R,5S)-4-methyl-5-phenyloxazolidin-2-one (4a, 75% yield) as a white solid. ^¹H NMR (400 MHz, CDCl₃): δ = 7.45-7.27 (m, 5 H), 7.05 (s, 1 H), 5.72 (d, J = 8.1 Hz, 1 H), 4.25 (m, 1 H), 0.83 (d, J = 6.6 Hz, 3 H) ppm. ^¹³C NMR (100 MHz, CDCl₃): δ = 159.8, 134.8, 128.2, 128.1, 125.7, 80.8, 52.2, 17.2 ppm. IR (NaCl): ν = 3240, 2980, 1756 cm^-¹. MS (EI⁺): m/z (%) = 239 (5) [M⁺], 107 (100), 104 (23). [α]_D ^²7 +162 (c 0.50, CHCl₃).
(R)-Ethyl 2-Oxothiazolidine-4-carboxylate (4h): ^¹H NMR (400 MHz, CDCl₃): δ = 7.06 (br s, 1 H), 4.39 (ddd, J = 8.4, 4.8, 1.0 Hz, 1 H), 4.18 (q, J = 7.1 Hz, 2 H), 3.64 (dd, J = 11.4, 8.4 Hz, 1 H), 3.51 (dd, J = 11.4, 4.8 Hz, 1 H), 1.23 (t, J = 3 × 7.1 Hz, 3 H) ppm. ^¹³C NMR (100 MHz, CDCl₃): δ = 174.8, 170.0, 62.0, 55.9, 31.6, 13.8 ppm. IR (NaCl): ν = 3263, 2983, 1741 cm^-¹. MS (EI⁺): m/z (%) = 175 (22), 102 (10), 74 (60). [α]_D ^²0 -53 (c 3.15, CHCl₃).

19

Unpublished results.

20 McGhee W. Riley D. J. Org. Chem.  1995,  60:  6205