Synthesis 2007(21): 3399-3405  
DOI: 10.1055/s-2007-990802
PAPER
© Georg Thieme Verlag Stuttgart · New York

New Synthetic Routes toward Enantiopure (2S,3R,4R)-4-Hydroxyisoleucine by 1,3-Dipolar Cycloaddition of a Chiral Nitrone to C4 Alkenes

Kaiss Aouadia,b, Erwann Jeanneauc, Moncef Msaddekb, Jean-Pierre Praly*a
a Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS), CNRS, UMR5246, Université Lyon 1, CPE Lyon, bâtiment 308, 43 boulevard du 11 Novembre 1918, F-69622 Villeurbanne, France
Fax: +33(4)72448349; e-Mail: jean-pierre.praly@univ-lyon1.fr;
b Laboratoire de Synthèse Hétérocyclique, Chimie des Substances Naturelles, Faculté des Sciences de Monastir, Université de Monastir, 5019 Monastir, Tunisia
c Centre de Diffractométrie Henri Longchambon, Université Lyon 1, Bât. Raulin, 43 Boulevard du 11 Novembre 1918, 69622 Villeurbanne, France
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Publikationsverlauf

Received 12 June 2007
Publikationsdatum:
16. Oktober 2007 (online)

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Abstract

1,3-Dipolar cycloaddition reaction of a chiral nitrone derived from (-)-menthone to E/Z mixtures of crotonaldehyde or (Z)-but-2-en-1,4-diol opens, by simultaneous creation of three contiguous asymmetric centers, new access to enantiopure (2S,3R,4R)-4-hydroxyisoleucine, respectively in 13% (7 steps) and 34% (6 steps) overall yield.

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Crystal data of compound (4R)-6: C17H29IN2O2, M = 420.33, orthorhombic, P212121, a = 8.761(5) Å, b = 10.744(5) Å, c = 20.202(5) Å, V = 1901.6(18) Å3, Z = 4, D x = 1.468 Mg m-3, µ (Mo-Kα) = 1.69 mm-1, F(000) = 856, colorless block, 0.05 × 0.05 × 0.05 mm, 4201 reflections measured (R int = 0.000), 4183 unique, wR 2 = 0.040, conventional R = 0.032 on F values of 3704 reflections with I > 2.0 σ(I), (Δ/σ)max = 0.001), S = 1.06 for all data and 200 parameters. Unit cell determination and intensity data collection (θmax = 27.83°) were performed on a Nonius KappaCCD at 293 (2) K. Structure solutions were found by direct methods and refinements were achieved by full-matrix least-squares methods on F. Further details of the crystal structure investigation can be obtained from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge, CB2 1EZ, UK (CCDC deposition no. 641986).
Crystal data of compound 11: C17H28I2N2O2, M = 546.23, orthorhombic, P212121, a = 8.116(5) Å, b = 8.878(5) Å, c = 28.745(5) Å, V = 2071.2(18) Å3, Z = 4, D x = 1.752 Mg m-3, µ (Mo-Kα) = 3.05 mm-1, F(000) = 1064, colorless prism, 0.39 × 0.25 × 0.23 mm, 9967 reflections measured (R int = 0.095), 4488 unique, wR 2 = 0.052, conventional R = 0.045 on F values of 2322 reflections with I > 2.0 σ(I), (Δ/σ)max = 0.001), S = 1.12 for all data and 209 parameters. Unit cell determination and intensity data collection (θmax = 27.83°) were performed on a Nonius KappaCCD at 293 (2) K. Further details of the crystal structure investigation can be obtained from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge, CB2 1EZ, UK (CCDC deposition no. 641985).