Synlett 2006(17): 2727-2730  
DOI: 10.1055/s-2006-950253
LETTER
© Georg Thieme Verlag Stuttgart · New York

Gold(I)-Catalyzed Formation of 5-Methylene-1,3-oxazolidin-2-ones

Andrea Buzas, Fabien Gagosz*
Laboratoire de Synthèse Organique, UMR CNRS 7652, Ecole Polytechnique, DCSO, 91128 Palaiseau, France
Fax: +33(1)69333851; e-Mail: [email protected];
Further Information

Publication History

Received 9 July 2006
Publication Date:
09 October 2006 (online)

Abstract

A study concerning the gold(I)-catalyzed rearrangement of propargylic tert-butylcarbamates into 5-methylene-1,3-oxazolidin-2-ones is described. The mild reaction conditions employed allow the efficient synthesis of a variety of these structures, which would be less conveniently obtained using other reported methods.

    References and Notes

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  • 12 These substrates substituted at the propargylic position (5i-n) were synthesized according to the method developed by Petrini and coworkers. See, for instance: Mecozzi T. Petrini M. J. Org. Chem.  1999,  64:  8970 
9

The work recently reported by Carretero and coworkers (see ref. 8) was only dealing with the synthesis of oxazolidinones substituted at the nitrogen and alkyne terminus.

10

Ozaxolidinone 6a could, however, be synthesized in 94% yield (3 h, CH2Cl2, r.t.) when the more electrophilic (p-CF3Ph)3PAuNTf2 catalyst (1 mol%) was used instead of PPh3AuNTf2.

11

Representative Experimental Procedure - Synthesis of 3-Benzyl-4,4-dimethyl-1,3-oxazolidin-2-one (6d).
To a solution of benzyl (1,1-dimethylprop-2-ynyl)carbamic acid tert-butyl ester (5d, 136 mg, 0.5 mmol) in 1 mL of CH2Cl2 was added PPh3AuNTf2 (3.7 mg, 0.005 mmol). The reaction mixture was stirred for 5 min, then filtered through a small pad of silica and the solvent was removed under reduced pressure. The residue was then purified by flash column chromatography (PE-EtOAc, 60:40) to give oxazolidinone 6d (108 mg, 99%, pale yellow solid); mp 69-70 °C. 1H NMR (400 MHz, CDCl3): δ = 7.39-7.27 (m, 5 H), 4.68 (d, J = 3.3 Hz, 1 H), 4.48 (s, 2 H), 4.25 (d, J = 3.3 Hz, 1 H), 1.33 (s, 6 H). 13C NMR (50 MHz, CDCl3): δ = 160.7, 154.8, 137.6, 128.6, 127.8, 127.7, 84.1, 61.5, 44.0, 27.6. IR (CCl4): 2979, 1786, 1692, 1663, 1393, 1054 cm-1. MS (CI + NH3): m/z = 235 [MNH4 +], 218 [MH+]. HRMS (EI): m/z calcd for C13H15O2N: 217.1103; found: 217.1103.