Download PDF
Synlett 2013; 24(17): 2266-2270
DOI: 10.1055/s-0033-1339681
letter
© Georg Thieme Verlag Stuttgart · New York

Activation of Hydrogen Peroxide by Diphenyl Diselenide for Highly Enantioselective Oxaziridinium Salt Mediated Catalytic Asymmetric Epoxidation

Benjamin R. Buckley*
a   Department of Chemistry, Loughborough University, Ashby Road, Loughborough, Leicestershire, LE11 3TU, UK   Fax: +44(1509)223925   Email: b.r.buckley@lboro.ac.uk
,
Claire E. Elliott
a   Department of Chemistry, Loughborough University, Ashby Road, Loughborough, Leicestershire, LE11 3TU, UK   Fax: +44(1509)223925   Email: b.r.buckley@lboro.ac.uk
,
Yohan Chan
b   School of Chemistry, University of East Anglia, Norwich, Norfolk NR4 7TJ, UK   Email: p.page@uea.ac.uk
,
Nicholas Dreyfus
c   Eli Lilly, Erl Wood Manor, Erl Wood, Windlesham, Surrey, UK
,
Philip C. Bulman Page*
b   School of Chemistry, University of East Anglia, Norwich, Norfolk NR4 7TJ, UK   Email: p.page@uea.ac.uk
› Author Affiliations
Further Information

Publication History

Received: 14 July 2013

Accepted after revision: 07 August 2013

Publication Date:
10 September 2013 (online)

    Permissions and Reprints All articles of this category


Abstract

The first reported use of benzeneperseleninic acid as a catalytic mediator for oxaziridinium ion catalysed epoxidation is described, providing reaction rates and ee values (up to 85%) similar to those reported when using oxone as the stoichiometric oxidant. A dual catalytic cycle is proposed, in which diphenyl diselenide is initially converted into the perseleninic acid, which in turn oxidises an iminium ion to the corresponding oxaziridinium species, thus facilitating asymmetric oxygen transfer to an alkene.

Key words

epoxidation - iminium salt - oxaziridinium - diphenyl diselenide - oxidation
 

  • References and Notes

    • 3a Page PC. B, Buckley BR, Rassias GA, Blacker AJ. Eur. J. Org. Chem. 2006; 803
    • 3b Page PC. B, Buckley BR, Appleby LF, Alsters PA. Synthesis 2005; 3405
      Thieme Connect
  • 4 See: http://www2.dupont.com/Oxone/en_US/.
  • 5 Campestrini S, Di Furia F, Labat G, Novello F. J. Chem. Soc., Perkin Trans. 2 1994; 2175
  • 7 Page PC. B, Buckley BR, Heaney H, Blacker AJ. Org. Lett. 2005; 7: 375
    CrossrefSearch in Google Scholar
  • 8 Page PC. B, Appleby LF, Day D, Chan Y, Buckley BR, Allin SM, Mckenzie MJ. Org. Lett. 2009; 11: 1991
    CrossrefSearch in Google Scholar
  • 9 Bartlett CJ, Day DP, Chan Y, Allin SM, McKenzie MJ, Slawin AM. Z, Page PC. B. J. Org. Chem. 2012; 77: 772
    CrossrefSearch in Google Scholar
  • 10 Page PC. B, Parker P, Rassias GA, Buckley BR, Bethell D. Adv. Synth. Catal. 2008; 350: 1867
    CrossrefSearch in Google Scholar
  • 11 Page PC. B, Parker P, Buckley BR, Rassias GA, Bethell D. Tetrahedron 2009; 65: 2910
    CrossrefSearch in Google Scholar
  • 12 Brodsky BH, Du Bois J. J. Am. Chem. Soc. 2005; 127: 15391
    CrossrefSearch in Google Scholar
    • 13a ten Brink G.-J, Vis J.-M, Arends IW. C. E, Sheldon RA. J. Org. Chem. 2001; 66: 2429
      CrossrefSearch in Google Scholar
    • 13b ten Brink G.-J, Fernandes BC. M, van Vliet MC. A, Arends IW. C. E, Sheldon RA. J. Chem. Soc., Perkin Trans. 1 2001; 224
  • 14 Page PC. B, Rassias GA, Barros D, Ardakani A, Bethell D, Merifield E. Synlett 2002; 580
  • 15 2,2′-Bis(bromomethyl)octahydrobinaphthalene was prepared according to the method of Ruan (see ref. 21). The dibromide (0.20 g, 0.45 mmol) and (S,S)-acetonamine (0.20 g, 0.45 mmol) were dissolved in MeCN (30 mL), and K2CO3 (0.185 g, 1.34 mmol) was added. The solution was stirred with heating under reflux for 4 h. After cooling to r.t., the solvent was removed under reduced pressure. The residue was dissolved in CH2Cl2 (30 mL), washed with H2O (2 × 30 mL), dried (MgSO4), filtered and solvents were removed under reduced pressure to afford 7 as a colourless solid (0.20 g, 91%); mp 170–171 ºC; [α]D 20 –8.4 (c = 0.9, CH2Cl2). IR (film): 3052, 2932, 1633, 1599, 1449, 1443, 1388, 1300, 1200, 1142, 1109, 950, 850, 731 cm–1. 1H NMR (400 MHz, CDCl3): δ = 1.59 (s, 3 H), 1.64 (s, 3 H), 1.74–1.78 (m, 8 H), 2.12–2.19 (m, 2 H), 2.62–2.65 (m, 3 H), 2.85 (t, J = 6.8 Hz, 4 H), 3.10 (d, J = 12.4 Hz, 2 H), 3.50 (d, J = 12.0 Hz, 2 H), 4.11–4.23 (m, 3 H), 6.90 (d, J = 7.2 Hz, 2 H), 6.99 (d, J = 7.2 Hz, 2 H), 7.26–7.32 (m, 5 H). 13C NMR (100 MHz, CDCl3): δ = 19.2, 22.7, 22.8, 23.0, 23.1, 27.6, 27.7, 29.5, 29.6, 52.8, 59.9, 61.3, 125.9, 126.7, 127.6, 128.0, 132.3, 133.5, 154.9, 137.8, 158.1, 138.7. HRMS (ESI): m/z [M + H+] calcd for C34H40NO2: 494.3059; found: 494.3043. Anal. Calcd for C34H39NO2: C, 82.72; H, 7.96; N, 2.84. Found: C, 82.52; H, 7.66; N, 2.92. Compound 7 (0.08 g, 0.16 mmol) was dissolved in CH2Cl2 (20 mL) and N-bromosuccinimide (0.04 g, 0.19 mmol, 1.2 equiv) was added. The solution was heated under reflux for 4 h. After cooling to r.t., the solvent was removed under reduced pressure. The residue was dissolved in EtOH, and sodium tetraphenylborate (0.06 g, 0.018 mmol, 1.1 equiv), dissolved in the minimum amount of MeCN, was added in one portion, and the reaction mixture was stirred for 5 min. The solvents were removed under reduced pressure to give a yellow residue that was recrystallised from hot EtOH to give 5 as a yellow crystalline solid, washed with cold EtOH and Et2O (0.10 g, 76%); mp 130–135 °C; [α]D 20 –10.0 (c = 0.8, CH2Cl2). IR (film): 3053, 2936, 1619, 1575, 1488, 1427, 1382, 1202, 1111, 838, 733, 703 cm–1. 1H NMR (400 MHz, CDCl3): δ = 1.55–1.62 (d, 6 H), 1.76–2.27 (m, 12 H), 2.53–2.99 (m, 6 H), 3.45–3.71 (m, 3 H), 5.00–5.05 (m, 1 H), 6.73–6.78 (m, 4 H), 6.84–7.11 (m, 10 H), 7.20–7.28 (m, 8 H), 7.29–7.36 (m, 8 H). 13C NMR (100 MHz, CDCl3; mixture of rotamers): δ = 14.2, 18.8, 18.9, 21.0, 21.8, 22.1, 22.2, 22.5, 22.8, 22.9, 23.3, 26.8, 27.8, 27.95, 28.02, 29.5, 29.6, 29.7, 29.6, 29.7, 30.2, 30.6, 30.9, 48.4, 54.8, 55.2, 60.4, 60.5, 63.2, 66.4, 71.7, 73.8, 99.1, 100.4, 122.3, 124.1, 124.7, 124.8, 125.1, 125.4, 125.8, 125.8, 125.9, 127.1, 128.0, 128.2, 128.4, 128.6, 128.8, 128.9, 129.0, 129.7, 130.5, 131.7, 133.8, 134.1, 134.6, 134.9, 135.2, 135.6, 135.8, 136.0, 136.1, 137.7, 138.8, 139.8, 140.4, 140.5, 144.0, 144.6, 146.3, 187.0. HRMS (EI): m/z [M+] calcd for iminium cation C34H38NO2: 492.2895; found: 492.2897. Anal. Calcd for C58H58BNO2: C, 85.80; H, 7.20; N, 1.73. Found: C, 85.45; H, 6.82; N, 1.63.
  • 16 General Procedure for Epoxidation using Diphenyl Diselenide, Hydrogen Peroxide and Iminium Salt or Amine: The alkene (1.0 equiv) was dissolved in MeCN (2 mL per mmol alkene), and the iminium salt (or amine) catalyst (5 mol%) was added along with diphenyl diselenide (1 mol%). The reaction vessel was cooled in an ice bath for 5 min, and hydrogen peroxide (50%, 3.0 equiv) was added dropwise over 5 min. The reaction progress was followed using TLC, and, when the reaction was complete, Et2O (20 mL) was added. The mixture was washed twice with H2O (2 ×) and once with sat. brine, and dried over MgSO4. The solvents were removed under reduced pressure, and the crude product was purified using column chromatography on silica gel (EtOAc–petroleum ether–Et3N).
  • 17 Aggarwal VK, Lopin C, Sandrinelli F. J. Am. Chem. Soc. 2003; 125: 7596
    Search in Google Scholar
  • 18 Ho C.-Y, Chen Y.-C, Wong M.-K, Yang D. J. Org. Chem. 2005; 70: 898
    CrossrefPubMedSearch in Google Scholar
  • 20 Grieco PA, Yokoyama Y, Gilman S, Ohfune Y. J. Chem. Soc., Chem. Commun. 1977; 870
  • 21 Ruan J, Lu G, Xu L, Li YM, Chan AS. C. Adv. Synth. Catal. 2008; 350: 76
    CrossrefSearch in Google Scholar