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Synlett 2002(6): 0952-0956
DOI: 10.1055/s-2002-31909
LETTER
© Georg Thieme Verlag Stuttgart · New York

N-Vinyl-2-Oxazolidinone: New Preparation Methods and First Uses as a Dienophile

Catherine Gaulon, Patricia Gizecki, Robert Dhal*, Gilles Dujardin*
UMR 6011 CNRS- Université du Maine, Laboratoire de Synthèse Organique (UCO2M)Faculté des Sciences, Avenue Olivier Messiaen, 72085 Le Mans Cedex 9, France
e-Mail: dujardin@univ-lemans.fr;
Further Information

Publication History

Received 6 March 2002
Publication Date:
07 February 2007 (online)

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Abstract

N-Vinyloxazolidinone was conveniently prepared in 73% overall yield by an easy two-step procedure based on the dehydroalkoxylation of an intermediate hemiaminal using trimethylsilyl trifluoromethanesulfonate and triethylamine. The good dienophilicity of this enecarbamate was demonstrated in several [4+2] stereocontrolled processes involving activated 1-oxabutadienes under appropriate Lewis-acid catalyzed conditions. In addition, an unexpected amido-alkylation of the title compound is described under mild conditions.

Key-words

N-vinyl oxazolidinone - N,O-acetal - lanthanide - dienophile - heterocycloaddition

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14

General preparation of hetero-adduct 4a-f with Eu(fod) 3 : A solution of heterodiene 3 (0.5 mmol), N-vinyl-2-oxazol-idinone 1 (0.5 mmol) and Eu(fod)3 (0.025 mmol) in cyclo-hexane (5 mL) was refluxed under nitrogen for the time referred to Table [2] . After removal of solvent the crude product was chromatographed (silica gel 40/1) using cyclohexane-AcOEt, 70:30 to 50:50. Compounds 4a-f obtained with yields referred to Table [2] are new and analytical data of one representative example is included in ref. 15.

15

Analytical data of hetero-adduct 4a cis: white crystal, mp 59-61 °C(ether); Rf = 0.23 (cyclohexane-AcOEt, 1:1); 1H NMR (400 MHz, CDCl3), δ 1.94 (dt, 1 H, J AB = 12.8 Hz,
J 2ax-3 = J 2ax-1 = 11.3 Hz, H-2ax), 2.26 (ddt, 1 H, J AB = 12.8 Hz, J 2eq-3 = 6.4 Hz, J 2eq-1 = J 2eq-4 = 2 Hz, H-2eq), 3.57 (dt, 1 H, JAB = J 4 ′ B-5 ′ B = 8.9 Hz, J 4 ′ B-5 ′ A = 6.2 Hz, H-4′B), 3.81 (s, 3 H, OCH3), 3.84 (m, 1 H, H-4′A), 3.89 (ddd, 1 H, J 3-2ax = 11.3 Hz, J 3-2eq = 6.4 Hz, J 3-4 = 2.5 Hz, H-3), 4.38 (dt, 1 H, J AB = J 5 ′ B-4 ′ B = 8.9 Hz, J 5 ′ B-4 ′ A = 6.9 Hz, H-5′B), 4.46 (dt, 1 H, JAB = J 5 ′ A-4 ′ A = 8.9 Hz, J 5 ′ A-4 ′ B = 6.2 Hz, H-5′A), 5.76 (dd, 1 H, J 1-2ax = 11.3 Hz, J 1-2eq = 2 Hz, H-1), 6.17 (t, 1 H, J 4-3 = J 4-2eq = 2 Hz, H-4), 7.22 (d, 2 H, J = 6.9 Hz, H o ), 7.29 (t, 1 H, J = 7.4 Hz, H p ), 7.35 (t, 2 H, J = 7.4 Hz, H m ); 13C NMR (100 MHz, CDCl3), δ 35.5 (C-2), 39.5 (C-3), 40.1 (C-4′), 52.7 (OCH3), 62.9 (C-5′), 81.3 (C-1), 114.6 (C-4), 127.5 (C o ), 127.7 (C p ), 129.3 (C m ), 142.5 (C n ), 144.4 (C-5), 157.8 (C-2′), 163.0 (CO2). IR(film): 1758 (C=O), 1643 (C=C), 1134, 1248, 1288 (C-O) cm-1; SM C16H17NO5 [M]+· 303 (1.8%); HRMS (EI) calcd for C16H15NO4 [M-H2O]+ 285.1001, found 285.1008.

16

Preparation of hetero-adduct 4a trans with SnCl 4 : To a cooled solution (-78 °C) of heterodiene 3a (95 mg, 0.5 mmol) and N-vinyl-2-oxazolidinone 1 (57 mg, 0.5 mmol) in anhydrous CH2Cl2 (5 mL) under nitrogen was added dropwise SnCl4 1 M in CH2Cl2 (0.25 mL, 0.25 mmol). After stirring (5 min) the mixture was quenched with sat. aq. NaHCO3 (5 mL). After returning to r.t. and extraction with CH2Cl2 (2 × 5 mL), the resulting organic layer was dried (MgSO4). Removal of solvent and purification by chromatography (silica gel 40/1; cyclohexane-AcOEt, 70:30 to 50:50) yielded 4a (143 mg, 94%) as a mixture cis/trans, 68:32. 4a trans was thus isolated as a white solid; Rf = 0.16 (cyclohexane-AcOEt, 1:1); 1H NMR (400 MHz, CDCl3), δ 2.03 (dq, 1 H, J AB = 13.3 Hz, J2eq-1 = J2eq-3 =
J 2eq-4 = 2 Hz, H-2eq), 2.33 (ddd, 1 H, J AB = 13.3 Hz, J 2ax-1 = 11.3 Hz, J 2ax-3 = 6.6 Hz, H-2ax), 3.61 (dt, 1 H, J AB = J 4 ′ B-5 ′ B = 8.6 Hz, J 4 ′ B-5 ′ A = 5.9 Hz, H-4′B), 3.81 (m, 2 H, H-3 + H-4′A), 3.83 (s, 3 H, OCH3), 4.34 (q, 1 H, JAB = J 5 ′ B-4 ′ B = J 5 ′ B-4 ′ A = 8.5 Hz, H-5′B), 4.42 (dt, 1 H, JAB = J 5 ′ A-4 ′ A = 8.9 Hz, J 5 ′ A-4 ′ B = 5.9 Hz, H-5′A), 5.43 (dd, 1 H, J 1-2ax = 11.3 Hz, J 1-2eq = 2.2 Hz,
H-1), 6.25 (dd, 1 H, J 4-3 = 5.3 Hz, J 4-2eq = 1.5 Hz, H-4), 7.23 (d, 2 H, J = 6.9 Hz, H o ), 7.27 (t, 1 H, J = 5.9 Hz, H p ), 7.35 (t, 2 H, J = 7.4 Hz, H m ); 13C NMR (100 MHz, CDCl3), δ 33.8 (C-2), 37.1 (C-3), 40.5 (C-4′), 52.7 (OCH3), 62.8 (C-5′), 77.7 (C-1), 111.9 (C-4), 127.6 (C p ), 128.4 C o ), 129.3 (C m ), 143.2 (C n ), 144.7 (C-5), 157.8 (C-2′), 163.1 (CO2).

20

Selected data of 9: 1H NMR (400 MHz, CDCl3), δ 6.87 (1 H, dd, J = 14.3 and 1.2 Hz), 5.13 (1 H, dd, J = 14.3 and 6.4 Hz).IR(film): 3309 (NH); 1747 (C=O), 1670 (C=C), 1637 (C=O) cm-1.