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

doi:10.1055/s-2005-871954

LETTER

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;

Abstract

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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

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References

<A NAME="RD10205ST-1A">1a</A> Ndkala AJ. Hashemzadeh M. So RC. Howell AR. Org. Lett. 2002, 4: 1719

<A NAME="RD10205ST-1B">1b</A> Tuch A. Saniere M. Le Merrer Y. Depezay JC. Tetrahedron: Asymmetry 1996, 7: 897

<A NAME="RD10205ST-2A">2a</A> Nakajima N. Isobe T. Irisa S. Ubukata M. Heterocycles 2003, 59: 107 ; and references cited therein

<A NAME="RD10205ST-2B">2b</A> Gravier-Pelletier C. Milla M. Le Merrer Y. Depezay JC. Eur. J. Org. Chem. 2001, 3089

<A NAME="RD10205ST-3A">3a</A> Takahata H. Banba Y. Sasatani M. Nemoto H. Kato A. Adachi I. Tetrahedron 2004, 60: 8199

<A NAME="RD10205ST-3B">3b</A> Singh OV. Han H. Tetrahedron Lett. 2003, 44: 2387

<A NAME="RD10205ST-3C">3c</A> Lee HK. Chun JS. Pak CS. Tetrahedron 2003, 59: 6445

<A NAME="RD10205ST-4A">4a</A> Baddorey R. Cativiela C. Diaz-de-Villegas MD. Diez R. Galvez JA. Eur. J. Org. Chem. 2003, 2268

<A NAME="RD10205ST-4B">4b</A> Merino P. Franco S. Merchan FL. Revuelta J. Tejero T. Tetrahedron Lett. 2002, 43: 459

<A NAME="RD10205ST-4C">4c</A> Harms G. Schaumann E. Adiwidjaja G. Synthesis 2001, 577

<A NAME="RD10205ST-4D">4d</A> Khiar N. Singh K. Garcia M. Martin-Lomas M. Tetrahedron Lett. 1999, 40: 5779

<A NAME="RD10205ST-4E">4e</A> Dequeker E. Compernolle F. Toppet S. Hoornaert G. Tetrahedron 1995, 51: 5877

<A NAME="RD10205ST-5A">5a</A> Behrens CH. Sharpless KB. J. Org. Chem. 1985, 50: 5696

<A NAME="RD10205ST-5B">5b</A> Roush WR. Adam MA. J. Org. Chem. 1985, 50: 3752

<A NAME="RD10205ST-6">6</A> Findeis MA. Whitesides GM. J. Org. Chem. 1987, 52: 2838

<A NAME="RD10205ST-7">7</A> Singh OV. Han H. Tetrahedron Lett. 2003, 44: 5289

<A NAME="RD10205ST-8A">8a</A> Greck C. Drouillat B. Thomassigny C. Eur. J. Org. Chem. 2004, 1377

<A NAME="RD10205ST-8B">8b</A> Greck C. Genêt JP. Synlett 1997, 741

<A NAME="RD10205ST-8C">8c</A> Genêt JP. Greck C. Lavergne D. Modern Amination Methods Ricci A. Wiley-VCH; Weinheim: 2000. p.65

<A NAME="RD10205ST-9">9</A> Kitamura M. Ohkuma S. Inoue S. Sayo N. Kumabayashi H. Akutagawa S. Ohta T. Tabaya H. Noyori R. J. Am. Chem. Soc. 1988, 110: 629

<A NAME="RD10205ST-10A">10a</A> Genêt JP. Ratovelomanana-Vidal V. Cano de Andrade MC. Pfister X. Guerreiro P. Lenoir JY. Tetrahedron Lett. 1995, 36: 4801

<A NAME="RD10205ST-10B">10b</A> Ratovelomanana-Vidal V. Genêt JP. Organomet. Chem. 1998, 567: 163

<A NAME="RD10205ST-11">11</A> Guanti G. Banfi L. Narisano E. Tetrahedron Lett. 1989, 30: 5507

<A NAME="RD10205ST-12">12</A> Nicolaou KC. Mitchell HJ. Fylaktakidou KC. Rodriguez RM. Suzuki H. Chem.-Eur. J. 2000, 6: 3116

<A NAME="RD10205ST-13">13</A> Fukuyama T. Laird AA. Hotchkiss LM. Tetrahedron Lett. 1985, 26: 6291

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.