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Synlett 2006(9): 1425-1427  
DOI: 10.1055/s-2006-939722
LETTER
© Georg Thieme Verlag Stuttgart · New York

N-Vinyl-1,3-oxazolidine-2-thiones as Dienophiles in Inverse Hetero-Diels-Alder Reactions: New Prospects for Asymmetric Induction

Sébastien Tardya, Arnaud Tatibouët*a, Patrick Rollina, Gilles Dujardinb
ICOA UMR 6005 CNRS, Université d’Orléans, 45067 Orléans, France, Fax: +33(2)38417281; e-Mail: arnaud.tatibouet@univ-orleans.fr; , UCO2M UMR 6011 CNRS, Université du Maine, 72085 Le Mans, France
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Publication History

Received 5 January 2006
Publication Date:
22 May 2006 (online)

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Abstract

Several N-vinyl-1,3-oxazolidine-2-thione (N-vinyl OZT) were conveniently used as new dienophiles in Eu(fod)3-catalyzed reverse hetero-Diels-Alder reactions involving benzylidene pyruvic acid methyl ester. Simple chiral N-vinyl OZT analogues homogeneously led to moderate endo and facial diastereoselectivities, when compared to those obtained with the corresponding N-vinyl-1,3-oxazolidin-2-ones. In contrast, high diastereocontrols were ­observed with a sugar-derived N-vinyl OZT.

Key words

oxazolidinethiones - hetero-Diels-Alder - enamide

    References and Notes

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2

Gaulon, C.; Dhal, R.; Chapin, T.; Dujardin, G. unpublished results.

9

Tardy, S.; Tatibouët, A.; Rollin, P. unpublished results.

10

Compound 8 endo I: [α]D 20 +50 (c 1.0, CHCl3). 1H NMR (CDCl3): δ = 1.33, 1.36, 1.47 (3 s, 12 H, CH 3), 1.85 (dt, J AB = 12.8 Hz, J 2ax ′ -3 ′ = J 2ax ′ -1 ′ = 11.3 Hz, 1 H, H2ax ′), 2.36 (ddt, J AB = 12.8 Hz, J 2eq ′ -3 ′ = 6.3 Hz, J 2eq ′ -1 ′ = J 2eq ′ -4 ′ = 1.8 Hz, 1 H, H2eq ′), 3.38 (d, J AB = 10.0 Hz, 1 H, H7b), 3.79 (s, 3 H, H7 ′), 3.80-4.00 (m, 2 H, H6b, H3 ′), 4.17-4.80 (m, 4 H, H4, H5, H6a, H7a), 4.38 (d, J 2-1 = 3.5 Hz, 1 H, H2), 5.70 (d, J 1-2 = 3.5 Hz, 1 H, H1), 6.20 (t, J 4 ′ -3 ′ = J 4 ′ -2eq ′ = 1.6 Hz, 1 H, H4 ′), 6.29 (dd, J 1 ′ -2ax ′ = 11.3 Hz, J 1 ′ -2eq ′ = 1.8 Hz, 1 H, H1 ′), 7.18-7.41 (m, 5 H, H-arom.) ppm. 13C NMR (CDCl3): δ = 25.1, 26.6, 26.8, 31.1 (CH3), 34.4 (C-2′), 38.6 (C-3′), 47.0 (C-7), 52.4 (C-7′), 68.2 (C-6), 73.2 (C-5), 77.4 (C-4), 83.5 (C-3), 83.9 (C-2), 88.3 (C-1′), 103.2 (C-1), 110.5, (CIV-iPrd), 114.4 (C-4′), 114.9 (CIV-iPrd), 127.2 (C-o′), 127.5 (C-p′), 129.1 (C-m′), 142.0 (C-n′), 144,0 (C-5′), 162.4 (C-6′), 186.8 (C=S) ppm. MS (IS): m/z = 548.5 [M + H]+.

11

Compound 8 endo II: [α]D 20 -26 (c 0.5, CHCl3). 1H NMR (CDCl3): δ = 1.17, 1.37, 4.41, 1.62 (4 s, 12 H, CH 3), 1.86 (dt, J AB = 12.8 Hz, J 2ax ′ -3 ′ = J 2ax ′ -1 ′ = 11.3 Hz, 1 H, H2ax ′), 2.37 (ddt, J AB = 12.8 Hz, J 2eq ′ -3 ′ = 6.5 Hz, J 2eq ′ -1 ′ = J 2eq ′ -4 ′ = 1.8 Hz, 1 H, H2eq ′), 3.69 (d, J AB = 10.3 Hz, 1 H, H7b), 3.82 (s, 3 H, H7 ′), 3.90-4.00 (m, 4 H, H3 ′, H5, H7a, H6b), 4.09 (dd, J AB = 7.3 Hz, J 6a-5 = 2.8 Hz, 1 H, H6a), 4.17 (d, J 4-5 = 8.5 Hz, 1 H, H4), 4.59 (d, J 2-1 = 3.5 Hz, 1 H, H2), 5.71 (d, J 1-2 = 3.5 Hz, 1 H, H1), 6.21 (t, J 4 ′ -3 ′ = J 4 ′ -2eq ′ = 1.6 Hz, 1 H, H4 ′), 6.32 (dd,
J 1 ′ -2ax ′ = 11.3 Hz, J 1 ′ -2eq ′ = 1.8 Hz, 1 H, H1 ′), 7.18-7.40 (m, 5 H, H-arom.) ppm. 13C NMR (CDCl3): δ = 25.4, 26.6, 27.0, 31.1 (CH3), 33.7 (C-2′), 38.6 (C-3′), 46.6 (C-7), 52.5 (C-7′), 68.6 (C-6), 73.9 (C-5), 77.4 (C-4), 84.0 (C-2), 84.2 (C-3), 88.3 (C-1′), 103.2 (C-1), 110.6, (CIV-iPrd), 114.8 (C-4′, CIV-iPrd), 127.2 (C-o′), 127.5 (C-p′), 129.1 (C-m′), 142.0 (C-n′), 143.8 (C-5′), 162.4 (C-6′), 186.2 (C=S) ppm. MS (IS): m/z = 548.5 [M + H]+.