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Synlett 2005(13): 2086-2088  
DOI: 10.1055/s-2005-871954
LETTER
© Georg Thieme Verlag Stuttgart · New York

Enantio- and Diastereoselective Syntheses of Orthogonally Protected anti-2-Amino-1,3,4-butanetriols from an Achiral β-Ketoester

Yann Bourdreux, Bruno Drouillat, Christine Greck*
Laboratoire SIRCOB, UMR 8086, Université de Versailles Saint-Quentin-en-Yvelines,, 45 avenue des Etats-Unis, 78035 Versailles Cédex, France
Fax: +33(1)39254452; e-Mail: greck@chimie.uvsq.fr;
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Publication History

Received 15 April 2005
Publication Date:
12 July 2005 (online)

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Abstract

An efficient enantio- and diastereoselective synthesis of orthogonally protected anti-2-amino-1,3,4-butanetriols from an achiral source is described. The anti relationship between the two adjacent aminated and hydroxylated carbons was controlled by sequential hydrogenation of a β-ketoester in the presence of a chiral ruthenium catalyst and electrophilic amination of the resulting β-hydroxyester.

Key words

aminobutanetriols - asymmetric synthesis - chiral ruthenium catalyst - electrophilic amination - orthogonal protecting groups

14

Characterization of Selected New Compounds: Compound 8: [α]D 25 -13 (c 0.52, EtOH). 1H NMR (300 MHz, CDCl3): δ = 7.36-7.33 (m, 5 H), 5.43 (d, 1 H, J = 6.4 Hz), 4.75 (d, 1 H, J = 11.7 Hz), 4.62 (d, 1 H, J = 11.7 Hz), 3.92-3.80 (m, 4 H), 3.71-3.63 (m, 2 H), 2.40 (s, 1 H), 1.43 (s, 9 H), 1.08, 1.07 (2 s, 21 H). 13C NMR (50 MHz, CDCl3): δ = 156.1, 138.0, 128.5, 127.9, 127.8, 80.3, 79.4, 72.9, 64.2, 63.1, 52.9, 28.3, 18.0, 11.8. Anal. Calcd for C25H45NO5Si: C, 64.20; H, 9.70; N, 2.99. Found: C, 64.43; H, 9.78; N, 2.85.
Compound 9a: [α]D 25 -12 (c 0.81, EtOH). 1H NMR (300 MHz, CDCl3): δ = 8.01 (m, 2 H), 7.61-7.52 (m, 1 H), 7.44-7.41 (m, 2 H), 7.34-7.28 (m, 5 H), 5.24 (d, 1 H, J = 9.1 Hz), 4.78 (d, 1 H, J = 11.8 Hz), 4.62 (d, 1 H, J = 11.8 Hz), 4.49-4.37 (m, 2 H), 4.34-4.21 (m, 1 H), 3.95 (m, 2 H), 3.72-3.66 (m, 1 H), 1.40 (s, 9 H), 1.09, 1.08 (2 s, 21 H). 13C NMR (75 MHz, CDCl3): δ = 166.4, 155.5, 138.2, 133.5, 132.9, 130.1, 129.7, 128.4, 128.3, 127.9, 127.7, 79.3, 78.9, 72.8, 64.5, 64.2, 50.7, 28.3, 18.0, 11.8. Anal. Calcd for C32H49NO6Si: C, 67.21; H, 8.64; N, 2.45. Found: C, 67.41; H, 8.89; N, 2.41.
Compound 9b: [α]D 25 -1.2 (c 0.50, EtOH). 1H NMR (300 MHz, CDCl3): δ = 7.26 (s, 5 H), 6.83 (s, 4 H), 5.34 (d, 1 H, J = 8.1 Hz), 4.78 (d, 1 H, J = 11.4 Hz), 4.71 (d, 1 H, J = 11.4 Hz), 4.18 (dd, 1 H, J = 9.2, 3.5 Hz), 4.15-4.04 (m, 1 H), 4.00-3.91 (m, 3 H), 3.78 (s, 3 H), 3.76-3.71 (m, 1 H), 1.43 (s, 9 H), 1.10, 1.08 (2 s, 21 H). 13C NMR (75 MHz, CDCl3): δ = 155.5, 154.0, 152.8, 138.5, 128.3, 127.9, 127.5, 115.5, 114.7, 79.3, 78.9, 73.1, 67.5, 65.2, 55.8, 51.0, 28.4, 18.0, 11.9. Anal. Calcd for C32H51NO6Si: C, 66.98; H, 8.96; N, 2.44. Found: C, 66.91; H, 8.84; N, 2.39.