Enantioselective Sulfide Oxidation with H2O2: A Solid Phase and Array Approach for the Optimisation of Chiral Schiff Base-Vanadium Catalysts

Béatrice Pelotier; Mike S. Anson; Ian B. Campbell; Simon J. F. Macdonald; Ghislaine Priem; Richard F. W. Jackson

doi:10.1055/s-2002-32582

LETTER

Enantioselective Sulfide Oxidation with H₂O₂: A Solid Phase and Array Approach for the Optimisation of Chiral Schiff Base-Vanadium Catalysts

Béatrice Pelotier^a, Mike S. Anson*^a, Ian B. Campbell^b, Simon J. F. Macdonald^b, Ghislaine Priem^b, Richard F. W. Jackson^c
^a GlaxoSmithKline, Medicines Research Centre, Chemical Development, Gunnels Wood Road, Stevenage, Hertfordshire SG1 2NY, UK
Fax: +44(134)8764414; e-Mail: msa17004@gsk.com;
^b GlaxoSmithKline, Medicines Research Centre, Medicinal Chemistry, Gunnels Wood Road, Stevenage, Hertfordshire SG1 2NY, UK
^c Department of Chemistry, Dainton Building, University of Sheffield
e-Mail: Brook Hill, Sheffield, S3 7HF, UK;

Abstract

All articles of this category

Abstract

Two libraries of chiral Schiff base ligands were synthesised and screened in the vanadium-catalysed oxidation of alkyl aryl sulfides with hydrogen peroxide as terminal oxidant. The vanadium-chiral Schiff base complex 10, readily prepared from 3,5-diiodo-salicylaldehyde and (S)-tert-leucinol, was found to be highly enantioselective. Optically active sulfoxides could thus be obtained in good yields with up to 97% ee.

Key words

asymmetric catalysis - Schiff bases - hydrogen peroxide - enantioselective sulfoxidation - supported catalysts

Full Text

References

<A NAME="RD10002ST-1">1</A> Carreño MC. Chem. Rev. 1995, 95: 1717

<A NAME="RD10002ST-2A">2a</A> Pezet F. Aït-Haddou H. Daran J.-C. Sasaki I. Balavoine GGA. Chem. Commun. 2002, 510

<A NAME="RD10002ST-2B">2b</A> Hiroi K. Suzuki Y. Abe I. Kawagishi R. Tetrahedron 2000, 56: 4701

<A NAME="RD10002ST-2C">2c</A> Tokunoh R. Sodeoka M. Aoe K.-I. Shibasaki M. Tetrahedron Lett. 1995, 36: 8035

Examples of biologically active sulfoxides:

<A NAME="RD10002ST-3A">3a</A> RP 73163: Pitchen P. Chem. Ind. (London) 1994, 16: 636

<A NAME="RD10002ST-3B">3b</A> Pantoprazole: Tanaka M. Yamazaki H. Hakusui H. Nakamichi N. Sekino H. Chirality 1997, 9: 17

<A NAME="RD10002ST-3C">3c</A> Ustiloxine: Hutton CA. White JM. Tetrahedron Lett. 1997, 38: 1643

<A NAME="RD10002ST-3D">3d</A> OPC-29030: Morita S. Matsubara J. Otsubo K. Kitano K. Ohtani T. Kawano Y. Uchida M. Tetrahedron: Asymmetry 1997, 8: 3707

<A NAME="RD10002ST-3E">3e</A> Methionine Sulfoxide: Holland HL. Brown FM. Tetrahedron: Asymmetry 1998, 9: 535

<A NAME="RD10002ST-3F">3f</A> Omeprazole: von Unge S. Langer V. Sjölin L. Tetrahedron: Asymmetry 1997, 8: 1967

<A NAME="RD10002ST-3G">3g</A> Esomeprazole: Cotton H. Elebring T. Larsson M. Li L. Sörensen H. von Unge S. Tetrahedron: Asymmetry 2000, 11: 3819

<A NAME="RD10002ST-3H">3h</A> ZD3638: Moseley JD. Moss WO. Welham MJ. Org. Process Res. Dev. 2001, 5: 491

<A NAME="RD10002ST-4A">4a</A> Kagan H. In Catalytic Asymmetric Synthesis Ojima I. Wiley-VCH; New York: 2000. Chap. 6c.

<A NAME="RD10002ST-4B">4b</A> Kagan H. In Asymmetric Oxidation reactions: Practical Approach in Chemistry Katsuki T. Oxford University press; Oxford: 2001. Chap. 4.1.

<A NAME="RD10002ST-5">5</A> Pitchen P. Duñach E. Deshmukh MN. Kagan HB. J. Am. Chem. Soc. 1984, 106: 8188

<A NAME="RD10002ST-6">6</A> Di Furia F. Modena G. Seraglia R. Synthesis 1984, 325

<A NAME="RD10002ST-7A">7a</A> Brunel J.-M. Kagan HB. Synlett 1996, 404

<A NAME="RD10002ST-7B">7b</A> Brunel J.-M. Kagan HB. Bull. Soc. Chim. Fr. 1996, 133: 1109

<A NAME="RD10002ST-8A">8a</A> Donnoli MI. Superchi S. Rosini C. J. Org. Chem. 1998, 63: 9392

<A NAME="RD10002ST-8B">8b</A> Bonchio M. Licini G. Di Furia F. Mantovani S. Modena G. Nugent WA. J. Org. Chem. 1999, 64: 1326

<A NAME="RD10002ST-8C">8c</A> Martyn LJP. Pandiaraju S. Yudin AK. J. Organomet. Chem. 2000, 603: 98

<A NAME="RD10002ST-8D">8d</A> Kokubo C. Katsuki T. Tetrahedron 1996, 52: 13895

<A NAME="RD10002ST-8E">8e</A> Peng Y. Feng X. Cui X. Jiang Y. Chan ASC. Synth. Commun. 2001, 31: 2287

<A NAME="RD10002ST-8F">8f</A> Alcón MJ. Corma A. Iglesias M. Sánchez F. J. Mol. Catal. A: Chem. 2002, 178: 253

<A NAME="RD10002ST-9A">9a</A> Mekmouche Y. Hummel H. Ho RYN. Que L. Schünemann V. Thomas F. Trautwein AX. Lebrun C. Gorgy K. Leprêtre J.-C. Collomb M.-N. Deronzier A. Fontecave M. Ménage S. Chem.-Eur. J. 2002, 8: 1196

<A NAME="RD10002ST-9B">9b</A> Saito B. Katsuki T. Tetrahedron Lett. 2001, 42: 3873

<A NAME="RD10002ST-9C">9c</A> Brinksma J. La Crois R. Feringa BL. Donnoli MI. Rosini C. Tetrahedron Lett. 2001, 42: 4049

<A NAME="RD10002ST-10A">10a</A> Bolm C. Bienewald F. Angew. Chem., Int. Ed. Engl. 1995, 34: 2640

<A NAME="RD10002ST-10B">10b</A> Vetter AH. Berkessel A. Tetrahedron Lett. 1998, 39: 1741

<A NAME="RD10002ST-10C">10c</A> Skarzewski J. Ostrycharz E. Siedlecka R. Tetrahedron: Asymmetry 1999, 10: 3457

<A NAME="RD10002ST-10D">10d</A> Karpyshev NN. Yakovleva OD. Talsi EP. Bryliakov KP. Tolstikova OV. Tolstikov AG. J. Mol. Catal. A: Chem. 2000, 157: 91

<A NAME="RD10002ST-10E">10e</A> Ohta C. Shimizu H. Kondo A. Katsuki T. Synlett 2002, 161

<A NAME="RD10002ST-11">11</A> Green SD. Monti C. Jackson RFW. Anson MS. Macdonald SJF. Chem. Commun. 2001, 2594

<A NAME="RD10002ST-12">12</A> Bryliakov KP. Karpyshev NN. Fominsky SA. Tolstikov AG. Talsi EP. J. Mol. Catal. A: Chem. 2001, 171: 73

Compound 5: ¹H NMR (CDCl₃, 250 MHz) δ = 10.30 (s, 1 H), 7.15 (m, 2 H), 6.08 (ddt, 1 H, J = 17.0, 10.5, 5.0 Hz), 5.52 (dd, 1 H, J = 17.0, 1.5 Hz), 5.33 (dd, 1 H, J = 10.5, 1.5 Hz), 4.46 (br. d, 2 H, J = 5.0 Hz), 3.98 (br. t, 2 H, J = 5.0 Hz), 2.46 (br. t, 2 H, J = 7.0 Hz), 1.85 (m, 4 H), 1.41 (s, 9 H); ¹³C NMR (CDCl₃, 62 MHz) δ = 190.4, 179.2, 156.5, 154.8, 145.6, 132.7, 130.3, 122.5, 117.5, 108.3, 79.9, 67.7, 35.2, 33.5, 30.7 (3 C), 28.5, 21.4; MS (ES) m/z = 335 (M + H⁺), 279, 251, 233.

<A NAME="RD10002ST-14">14</A> Hofsløkken NU. Skattebøl L. Acta Chem. Scand. 1999, 53: 258

Chiral amino acids failed to react with supported salicylaldehyde 6.

Typical procedure: Solid supported Schiff base 7 (6 µmol, 0.012 equiv) was weighed in an Alltech tube and the resin was swollen in CH₂Cl₂ for 1 h. A 0.04 M solution of VO(acac)₂ in CH₂Cl₂ (1 mL, 40 µmol) was added and the mixture was shaken for 1 h. The solution was filtered and the resin washed with CH₂Cl₂ (5 × 2 mL) and transferred into a reaction test tube. A 0.5 M solution of thioanisole (1 mL, 0.5 mmol, 1 equiv) and 1,2,3-trimethoxybenzene (0.1 mmol, 0.2 equiv, internal standard) in CH₂Cl₂ was added, followed by 7% H₂O₂ in H₂O (240 µL, 1.1 equiv). The reaction mixture was stirred for 16 h and analysed by chiral HPLC (Chiralcel OD-H, 5% EtOH in heptane, 1 mL/min, 227 nm). Retention times: 4.2 min(thioanisole), 7.1 min (internal standard), 11.7 min (R-methyl-phenylsulfoxide), 13.1 min (S-methyl-phenylsulfoxide), 14.3 min (methyl-phenylsulfone).

<A NAME="RD10002ST-17A">17a</A> Canali L. Cowan E. Deleuze H. Gibson CL. Sherrington DC. J. Chem. Soc., Perkin Trans. 1 2000, 2055

<A NAME="RD10002ST-17B">17b</A> Reger TS. Janda KD. J. Am. Chem. Soc. 2000, 122: 6929

<A NAME="RD10002ST-17C">17c</A> Sigman MS. Jacobsen EN. J. Am. Chem. Soc. 1998, 120: 4901

4-Bromo-1-hydroxy-2-naphthaldehyde was prepared by bromination of 1-hydroxy-2-naphthaldehyde with N-bromosuccinimide according to a literature procedure [19] and isolated in 60% yield. Spectroscopic data: ¹H NMR (CDCl₃, 250 MHz) δ = 12.60 (s, 1 H), 9.92 (s, 1 H), 8.49 (d, 1 H, J = 8.5 Hz), 8.19 (d, 1 H, J = 8.5 Hz), 7.80 (t, 1 H, J = 8.5 Hz), 7.80 (s, 1 H), 7.63 (t, 1 H, J = 8.5 Hz); ¹³C NMR (CDCl₃, 62 MHz) δ = 195.2, 161.3, 135.5, 131.8, 129.4, 127.2, 126.9, 125.8, 124.8, 114.8, 112.1.

<A NAME="RD10002ST-19">19</A> Boehlow TR. Harburn JJ. Spilling CD. J. Org. Chem. 2001, 66: 3111

Compound 10: ¹H NMR (CDCl₃, 250 MHz) δ = 14.85 (br. s, 1 H), 8.10 (s, 1 H), 8.00 (d, 1 H, J = 2.0 Hz), 7.51 (d, 1 H, J = 2.0 Hz), 3.99 (dd, 1 H, J = 11.5, 2.5 Hz), 3.69 (dd, 1 H, J = 11.5, 9.5 Hz), 3.07 (dd, 1 H, J = 9.5, 2.5 Hz), 1.00 (s, 9 H); ¹³C NMR (CDCl₃, 62 MHz) δ = 166.5, 164.6, 149.9, 141.0, 117.0, 92.6, 78.2, 75.9, 61.8, 32.9, 26.8 (3 C); MS (ES) m/z = 474 (M + H⁺).

Compound 11: ¹H NMR (CDCl₃, 250 MHz) δ = 13.57 (br. s, 1 H), 8.39 (d, 1 H, J = 8.0 Hz), 7.98 (d, 1 H, J = 8.0 Hz), 7.70 (m, 1 H), 7.67 (t, 1 H, J = 8.0 Hz), 7.49 (t, 1 H, J = 8.0 Hz), 7.01 (s, 1 H), 4.06 (dd, 1 H, J = 11.5, 3.0 Hz), 3.76 (br. t, 1 H, J = 10.5 Hz), 3.16 (m, 1 H), 1.07 (s, 9 H); ¹³C NMR (CDCl₃, 62 MHz) δ = 177.1, 162.2, 135.9, 131.5, 130.7, 127.7, 126.1, 125.5, 109.4, 107.0, 75.2, 62.3, 33.5, 27.2 (3 C); MS (ES) m/z = 350 and 352 (M + H⁺).

Typical experimental procedure: To a 0.03 M solution of ligand in CH₂Cl₂ (0.25 mL, 7.5 µmol, 0.015 equiv) was added a 0.02 M solution of VO(acac)₂ in CH₂Cl₂ (0.25 mL, 5 µmol, 0.01 equiv) and the resulting mixture was stirred at r.t. for 30 min. A 1 M solution of sulfide in CH₂Cl₂ (0.5 mL, 0.5 mmol, 1 equiv) was added and after 30 min stirring at r.t., the reaction mixture was cooled down to 0 °C. After 15 min at 0 °C, 27% H₂O₂ in H₂O (65 µL, 1.2 mmol, 1.2 equiv) was added dropwise. The mixture was stirred at 0 °C for 16 h and the solvent evaporated. The crude residue was purified by column chromatography (silica gel, EtOAc-cyclohexane).