Synlett 2013; 24(19): 2581-2585
DOI: 10.1055/s-0033-1340164
letter
© Georg Thieme Verlag Stuttgart · New York

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

Shabbair Mohammad
a  CNRS 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
a  CNRS 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
b  ICMMO, UMR 8182, Bât. 410, Université Paris-Sud 11, 15 rue Georges Clemenceau, 91405 Orsay Cedex, France
,
Carine Vaxelaire
a  CNRS 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
a  CNRS 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
a  CNRS 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*
a  CNRS 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
Further Information

Publication History

Received: 31 July 2013

Accepted after revision: 02 September 2013

Publication Date:
18 October 2013 (online)


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.

Supporting Information

 
  • References and Notes

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  • 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:
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  • 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).