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Synlett 2004(1): 125-127  
DOI: 10.1055/s-2003-43339
LETTER
© Georg Thieme Verlag Stuttgart · New York

Synthesis of a 5-oxo-2-Tetrahydrofuranyl Derivative of an Evans Auxiliary via a Novel Reaction Induced by Nucleophiles

Yikang Wu*, Liang Li, Ya-Ping Sun
State Key Laboratory of Bio-Organic & Natural Products Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Road, Shanghai 200032, P. R. China
Fax: +86(21)64166128; e-Mail: yikangwu@mail.sioc.ac.cn;
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Publication History

Received 12 October 2003
Publication Date:
26 November 2003 (online)

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Abstract

A 5-oxo-2-tetrahydrofuranyl derivative of an Evans auxiliary could be obtained through a previously unknown ‘rearrangement’ of the oxazolidinone moiety in an α-benzoxy-γ-aldehyde acyl oxazolidinone in 60-97% yields on treatment with a range of ­nucleophiles.

Key words

chiral auxiliaries - rearrangements - lactones - ring closure - tandem reactions

    References

  • 1 Fuber M. Herbert JM. Taylor RJK. J. Chem. Soc., Perkin Trans. 1  1989,  683 
    CrossrefGoogle Scholar
  • See for example:
  • 5a Evans DA. Science  1988,  240:  420 
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  • 5b Compendium of Chiral Auxiliary Applications   Vol. 1-3:  Roos G. Academic Press; San Diego: 2002. and many references cited therein
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  • 6 Wissing E. Kleijn H. Boersma J. van Koten G. Recl. Trav. Chim. Pays-Bas  1993,  112:  618 ; and references therein.
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2

Data for 5a: A white solid, mp 107-109 °C; [α]D 15 -190.0 (c 1.0, CHCl3). 1H NMR (300 MHz, CDCl3): δ = 7.50-7.20 (m, 10 H, aromat), 5.34 (dd, J = 9.0, 3.3 Hz, 1 H, H-2), 5.03 (t, J = 8.9 Hz, 1 H, H-7), 4.94 (d, J = 11.2 Hz, 1 H, H-8), 4.65 (d, J = 11.4 Hz, 1 H, H-8), 4.64-4.58 (m, 2 H, H-4 and H-6), 4.13 (t, J = 9.1 Hz, 1 H, H-6), 3.08 (ddd, J = 3.2, 8.6, 14.1 Hz, 1 H, H-3), 2.38 (ddd, J = 6.5, 8.9, 14.7 Hz, 1 H, H-3). 13C NMR (75 MHz, CDCl3): δ = 173.96 (C-1), 156.41 (C-5), 136.86 (q, aromat), 135.83 (q, aromat), 129.70, (aromat, CH), 129.57 (2 C, aromat), 128.42 (2 C, aromat), 128.08 (2 C, aromat), 128.01(aromat), 127.30 (2 C, aromat), 81.95 (C-2), 72.59 (C-4), 72.52 (C-8), 70.08 (C-6), 60.69 (C-7), 32.47 (C-3). FT-IR (film of highly conc. solution in CH2Cl2): 1764 cm-1. MS (EI): m/z (%) = 218(77) [M+ - BnOCHCH], 190(32), 164(33), 146(41), 130(27), 104(46), 91(100).

3

The crystallographic data (CCDC 207744) can be obtained free of charge via from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; e-mail: deposit@ccdc.cam.ac.uk.

4

Data for 5b(oil): [α]D 15 -113.8 (c 0.6, CHCl3). 1H NMR (300 MHz, CDCl3): δ = 7.50-7.20 (m, 10 H), 5.04 (dd, J = 9.1, 5.2 Hz, 1 H), 4.82 (d, J = 11.7 Hz, 1 H), 4.69 (t, J = 9.0 Hz, 1 H), 4.59 (d, J = 11.8 Hz, 1 H), 4.21-4.10 (m, 2 H), 2.24 (ddd, J = 5.5, 7.8, 19.1 Hz, 1 H), 1.81 (dt, J = 13.4, 10.0 Hz, 1 H). 13C NMR (75 MHz, CDCl3): δ = 172.66, 157.93, 139.27, 136.35, 129.60, 129.22, 128.49, 128.22, 128.13, 126.14, 81.36, 73.08, 72.51, 71.06, 55.40, 32.99. FT-IR(film): 1767 cm-1. MS (EI): m/z (%) = 218(48) [M+ - BnOCHCH], 190 (21), 164 (30), 146 (29), 130 (27), 104 (49), 91 (100).

7

It is interesting to note that treatment of 6 in anhydrous THF at -78 ºC with 4 did not give any 5 at all but a complicated product mixture.