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

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

• 1a Page PC. B, Farah MM, Buckley BR, Blacker AJ. J. Org. Chem. 2007; 72: 4424
• 1b Page PC. B, Buckley BR, Farah MM, Blacker AJ. Eur. J. Org. Chem. 2009; 3413
• 1c Page PC. B, Bartlett CJ, Chan Y, Day D, Parker P, Buckley BR, Rassias GA, Slawin AM. Z, Allin SM, Lacour J, Pinto A. J. Org. Chem. 2012; 77: 6128
• 1d Farah MM, Page PC. B, Buckley BR, Blacker AJ, Elsegood MR. J. Tetrahedron 2013; 69: 758
• 2a Picot A, Milliet P, Lusinchi X. Tetrahedron Lett. 1976; 1573
• 2b Milliet P, Picot A, Lusinchi X. Tetrahedron Lett. 1976; 1577
• 2c Hanquet G, Lusinchi X, Milliet P. Tetrahedron Lett. 1987; 28: 6061
• 2d Hanquet G, Lusinchi X, Milliet P. Tetrahedron Lett. 1988; 29: 3941
• 2e Bohé L, Hanquet G, Lusinchi M, Lusinchi X. Tetrahedron Lett. 1993; 34: 7271
• 2f Bohé L, Lusinchi M, Lusinchi X. Tetrahedron 1999; 55: 141
• 2g Bohé L, Kammoun M. Tetrahedron Lett. 2002; 43: 803
• 2h Bohé L, Kammoun M. Tetrahedron Lett. 2004; 45: 747
• 2i Aggarwal VK, Wang MF. Chem. Commun. 1996; 191
• 2j Armstrong A, Ahmed G, Garnett I, Gioacolou K. Synlett 1997; 1075
• 2k Armstrong A, Ahmed G, Garnett I, Gioacolou K, Wailes JS. Tetrahedron 1999; 55: 2341
• 2l Gluszynska A, Mackowska I, Rozwadowska MD, Sienniak W. Tetrahedron: Asymmetry 2004; 15: 2499
• 2m Biscoe MR, Breslow R. J. Am. Chem. Soc. 2005; 127: 10812
• 2n Minakata S, Takemiya A, Nakamura K, Ryu I, Komatsu M. Synlett 2000; 1810
• 2o Wong M.-K, Ho L.-M, Zheng Y.-S, Ho C.-Y, Yang D. Org. Lett. 2001; 3: 2587
• 2p Crosthwaite JM, Farmer VA, Hallett JP, Welton T. J. Mol. Catal. A: Chem. 2008; 279: 148
• 2q Lacour J, Monchaud D, Marsol C. Tetrahedron Lett. 2002; 43: 8257
• 2r Novikov R, Lacour J. Tetrahedron: Asymmetry 2010; 21: 1611
• 2s Novikov R, Vachon J, Lacour J. Chimia 2007; 61: 236
• 2t Vachon J, Lauper C, Ditrich K, Lacour J. Tetrahedron: Asymmetry 2006; 17: 2334
• 2u Vachon J, Perollier C, Monchaud D, Marsol C, Ditrich K, Lacour J. J. Org. Chem. 2005; 70: 5903
• 2v Vachon J, Rentsch S, Martinez A, Marsol C, Lacour J. Org. Biomol. Chem. 2007; 5: 501
• 2w Novikov R, Bernadelli K, Lacour J. Adv. Synth. Catal. 2008; 350: 1113
• 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
• 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
• 6a Page PC. B, Barros D, Buckley BR, Blacker AJ, Marples BA. Tetrahedron: Asymmetry 2005; 16: 3488
• 6b Page PC. B, Buckley BR, Barros D, Blacker AJ, Heaney H, Marples BA. Tetrahedron 2006; 62: 6607
• 6c Page PC. B, Buckley BR, Barros D, Blacker AJ, Marples BA, Elsegood MR. J. Tetrahedron 2007; 63: 5386
• 7 Page PC. B, Buckley BR, Heaney H, Blacker AJ. Org. Lett. 2005; 7: 375
• 8 Page PC. B, Appleby LF, Day D, Chan Y, Buckley BR, Allin SM, Mckenzie MJ. Org. Lett. 2009; 11: 1991
• 9 Bartlett CJ, Day DP, Chan Y, Allin SM, McKenzie MJ, Slawin AM. Z, Page PC. B. J. Org. Chem. 2012; 77: 772
• 10 Page PC. B, Parker P, Rassias GA, Buckley BR, Bethell D. Adv. Synth. Catal. 2008; 350: 1867
• 11 Page PC. B, Parker P, Buckley BR, Rassias GA, Bethell D. Tetrahedron 2009; 65: 2910
• 12 Brodsky BH, Du Bois J. J. Am. Chem. Soc. 2005; 127: 15391
• 13a ten Brink G.-J, Vis J.-M, Arends IW. C. E, Sheldon RA. J. Org. Chem. 2001; 66: 2429
• 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
• 18 Ho C.-Y, Chen Y.-C, Wong M.-K, Yang D. J. Org. Chem. 2005; 70: 898
• 19a Gonçlaves M.-H, Martinez A, Grass S, Page PC. B, Lacour J. Tetrahedron Lett. 2006; 47: 5297
• 19b Page PC. B, Farah MM, Buckley BR, Blacker AJ, Lacour J. Synlett 2008; 1381
• 19c Vachon J, Lauper C, Ditrich K, Lacour J. Tetrahedron: Asymmetry 2006; 17: 2334
• 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