Asymmetric Sharpless Dihydroxylation Reaction of Chiral Bishomoallylic Alcohols: Application to the Synthesis of the C1–C10–C5 Fragment of FR225654

Shabbair Mohammad; Sabrina Dhambri; Didier Gori; Carine Vaxelaire; Geoffroy Sorin; Janick Ardisson; Marie-Isabelle Lannou

doi:10.1055/s-0033-1340164

Synlett, Table of Contents

Synlett 2013; 24(19): 2581-2585
DOI: 10.1055/s-0033-1340164

letter

Asymmetric Sharpless Dihydroxylation Reaction of Chiral Bishomoallylic Alcohols: Application to the Synthesis of the C1–C10–C5 Fragment of FR225654

Shabbair Mohammad

^aCNRS UMR 8638, Faculté de Pharmacie, Université Paris Descartes, 4 Avenue de l’Observatoire, 75270 Paris Cedex 06, France Fax: +33(1)43291403 Email: marie-isabelle.lannou@parisdescartes.fr

,

Sabrina Dhambri

^aCNRS UMR 8638, Faculté de Pharmacie, Université Paris Descartes, 4 Avenue de l’Observatoire, 75270 Paris Cedex 06, France Fax: +33(1)43291403 Email: marie-isabelle.lannou@parisdescartes.fr

,

Didier Gori

^bICMMO, UMR 8182, Bât. 410, Université Paris-Sud 11, 15 rue Georges Clemenceau, 91405 Orsay Cedex, France

,

Carine Vaxelaire

^aCNRS UMR 8638, Faculté de Pharmacie, Université Paris Descartes, 4 Avenue de l’Observatoire, 75270 Paris Cedex 06, France Fax: +33(1)43291403 Email: marie-isabelle.lannou@parisdescartes.fr

,

Geoffroy Sorin

^aCNRS UMR 8638, Faculté de Pharmacie, Université Paris Descartes, 4 Avenue de l’Observatoire, 75270 Paris Cedex 06, France Fax: +33(1)43291403 Email: marie-isabelle.lannou@parisdescartes.fr

,

Janick Ardisson

^aCNRS UMR 8638, Faculté de Pharmacie, Université Paris Descartes, 4 Avenue de l’Observatoire, 75270 Paris Cedex 06, France Fax: +33(1)43291403 Email: marie-isabelle.lannou@parisdescartes.fr

,

Marie-Isabelle Lannou*

^aCNRS UMR 8638, Faculté de Pharmacie, Université Paris Descartes, 4 Avenue de l’Observatoire, 75270 Paris Cedex 06, France Fax: +33(1)43291403 Email: marie-isabelle.lannou@parisdescartes.fr

› Author Affiliations

Abstract

All articles of this category

Abstract

Toward the synthesis of FR225654, an antidiabetic natural product, the Sharpless asymmetric dihydroxylation of chiral bishomoallylic alcohols, never reported in the literature, was examined. Employing the pyrimidine class of ligands, a high level of matched diastereoselectivity was obtained. An application to the stereoselective synthesis of the C1–C10–C5 fragment of FR225654 was performed.

Key words

stereoselective synthesis - natural products - dihydroxylation - diols - diastereoselectivity

Full Text

References

References and Notes

1a Takase S, Shibata T, Hino M, Nakajima H. J. Antibiot. 2005; 58: 447
1b Ohtsu Y, Sasamura H, Shibata T, Hino M, Nakajima H. J. Antibiot. 2005; 58: 452
1c Ohtsu Y, Yoshimura S, Kinoshita T, Takase S, Nakajima H. J. Antibiot. 2005; 58: 479

For erythronolide, see for instance:

2a McGuire JM, Bunch RL, Anderson RC, Boaz HE, Flynn EH, Powell HM, Smith JW. Antibiot. Chemother. 1952; 2: 281

For lankanolide and lankamycin, see:

2b Keller-Schierlein W, Roncari G. Helv. Chim. Acta 1962; 45: 138
2c Gäumann E, Hütter R, Keller-Schierlein W, Neipp L, Prelog V, Zahner H. Helv. Chim. Acta 1960; 43: 601

For ent-homoabyssomycin, see:

2d Abdalla MA, Yadav PP, Dittrich BA, Schüffler A, Laatsch H. Org. Lett. 2011; 13: 2156

3a Kolb HC, VanNieuwenhze MS, Sharpless KB. Chem. Rev. 1994; 94: 2483
3b Kolb HC, Sharpless KB In Transition Metals for Organic Synthesis . Vol. 2. Beller M, Bolm C. Wiley-VCH; Weinheim: 2004

4 A single synthesis of triol 4 has been reported: Thomas EJ, Whitehead JW. F. J. Chem. Soc., Perkin Trans. 1 1989; 507

For the synthesis of olefin 5, see for instance:

5a Evans DA, Polniaszek RP, DeVries KM, Guinn DE, Mathre DJ. J. Am. Chem. Soc. 1991; 113: 7613
5b Tan Z, Liang B, Huo S, Shi J.-c, Negishi E.-i. Tetrahedron: Asymmetry 2006; 17: 512
5c Trost BM, Michaelis DJ, Charpentier J, Xu J. Angew. Chem. Int. Ed. 2012; 51: 204

6a Theurer M, Fischer P, Baro A, Nguyen G.-S, Kourist R, Bornscheuer U, Laschat S. Tetrahedron 2010; 66: 3814
6b Donohoe TJ, Johnson PD, Pye RJ, Keenan M. Org. Lett. 2005; 7: 1275
6c Donohoe TJ. Synlett 2002; 1223

7 Corey EJ, Noe MC, Ting AY. Tetrahedron Lett. 1996; 37: 1735

8a Bondar D, Liu J, Müller T, Paquette LA. Org. Lett. 2005; 7: 1813
8b In another paper, SAD of tert-butyltrimethylsilyl ether protected 4-methylpent-4-en-1-ol was reported, however, without mention of the ee of the resulting diol: O’Connor PD, Knight CK, Friedrich D, Peng X, Paquette LA. J. Org. Chem. 2007; 72: 1747

9 Lorenz M, Kalesse M. Org. Lett. 2008; 10: 4371
10 Typical Procedure for the Sharpless Asymmetric Dihydroxylation K₂CO₃ (415 mg, 3 mmol), K₃Fe(CN)₆ (1.18 g, 3 mol), K₂OsO₂(OH)₄ (4 mg, 0.01 mmol), ligand (0.025 mol), and MeSO₂NH₂ (95 mg, 1 mmol) were added to a vigorously magnetically stirred solution of olefin (1 mmol) in a 1:1 mixture of t-BuOH–H₂O (10 mL) at 0 °C. The reaction mixture was stirred at 0 °C and monitored by TLC. Upon completion, the reaction mixture was quenched with solid Na₂SO₃ (1.5 g), warmed to r.t., and stirred for an additional 60 min. The product was extracted with EtOAc, washed with brine, dried over MgSO₄, concentrated, and purified on silica gel to afford an inseparable mixture of the required diol and the corresponding diastereomer.Spectroscopic Data of Diol 14 (Major Isomer)�1H NMR (300 MHz, CDCl3): δ = 7.26 (d, J = 8.6 Hz, 2 H), 6.89 (d, J = 8.6 Hz, 2 H), 4.47 (s, 2 H), 3.80 (s, 3 H), 3.42 (dd, J = 4.2, 9.0 Hz, 1 H), 3.38 (d, J = 12.0 Hz, 1 H), 3.32 (d, J = 12.0 Hz, 1 H), 3.21 (m, 1 H), 2.11 (m, 1 H), 1.68 (dd, J = 7.8, 14.6 Hz, 1 H), 1.36 (dd, J = 3.3, 14.6 Hz, 1 H), 1.16 (s, 3 H), 0.93 (d, J = 6.9 Hz, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 159.1, 12 9.3, 113.7, 76.6, 72.8, 71.8, 70.9, 55.0, 4 4.3, 28.6, 23.5, 19.5 ppm.Spectroscopic Data of Diol 16 (Minor Isomer)1H NMR (300 MHz, CDCl3): δ = 7.26 (d, J = 8.6 Hz, 2 H), 6.89 (d, J = 8.6 Hz, 2 H), 4. 46 (s, 2 H ), 3.80 (s, 3 H), 3.48 (m, 1 H), 3.38 (d, J = 11.0 Hz, 1 H), 3.32 (d, J = 11.0 Hz, 1 H), 3.19 (m, 1 H), 1.95 (m, 1 H), 1.63 (dd, J = 6.0, 14.4 Hz, 1 H), 1.45 (dd, J = 4.8, 14.4 Hz, 1 H), 1.16 (s, 3 H), 0.95 (d, J = 6 . 9 Hz, 3 H) ppm. 13C NMR (75 MHz, CDCl3) δ = 159.1, 129.3, 113.7, 76.4, 72.6, 71.8, 69.0, 55.0, 44.0, 29.1, 24.3, 19.3 ppm. IR (neat): ν = 3360, 2932, 1611, 1513, 1462, 1246, 1033, 819, 771 cm–1. ESI-HRMS: m/z calcd for C15H24NaO4+ [MNa+]: 291.1567; found: 291.1570.�For spectroscopic data of all diols, see the Supporting Information.�

For the synthesis of (S)- and (R)-iodides 13, see for instance:

11a Heckrodt TJ, Mulzer J. Synthesis 2002; 1857
11b Haslett GW, Paterson I. Org. Lett. 2013; 15: 1338
11c For the typical procedure and spectroscopic data of substrates, see the Supporting Information.

12a Wang Y, Dong X, Larock RC. J. Org. Chem. 2003; 68: 3090
12b Hareau GP.-J, Koiwa M, Hikichi S, Sato F. J. Am. Chem. Soc. 1999; 121: 3640

13 For analytical data for 12 and 13, see the Supporting Information.
14 For the osmylation of (R)- and (S)-12 and (R)- and (S)-13 in the absence of chiral ligands, see general procedure (ref. 10), however, without ligand.
15 Analytical Data for 25 ¹H NMR (400 MHz, CDCl₃): δ = 4.28–4.01 (br s, 2 H), 3.56 (dd, J = 3.6, 10.5 Hz, 1 H), 3.27 (dd, J = 9.0, 10.5 Hz, 1 H), 2.40 (d, J = 16.8 Hz, 1 Hz), 2.33 (d, J = 16.8 Hz, 1 H), 1.93 (m, 1 H), 1.58 (m, 2 H), 1.28 (s, 3 H), 0.86 (d, J = 6.9 Hz, 3 H), 0.13 (s, 9 H) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 103.7, 87.9, 71.7, 68.9, 47.3, 36.1, 31.8, 25.4, 19.6, 0.1 ppm. IR (neat): ν = 3276, 2958, 2927, 2175, 1460, 1423, 1376, 1248, 1032, 758 cm^–1. ESI-HRMS: m/z calcd for C₁₂H₂₄NaO₂Si⁺ [MNa⁺]: 251.1438; found: 251.1439. The relative configuration of 25 was confirmed by NMR experiments (NOESY analysis) of the corresponding γ-lactone (Figure 2).

Supplementary Material

Supporting Information