Facile Epoxidation of α,β-Unsaturated Ketones with trans-3,5-Dihydroperoxy-3,5-dimethyl-1,2-dioxolane as an Efficient Oxidant

Abstract

Application of trans-3,5-dihydroperoxy-3,5-dimethyl-1,2-dioxolane as an efficient oxygen source has been explored in the epoxidation of trans-chalcones. The reactions proceed under mild conditions at room temperature in alkaline solution to afford the corresponding epoxides in excellent yields.

Key words

α,β-unsaturated ketone - epoxide - dihydroperoxide - trans-3,5-dihydroperoxy-3,5-dimethyl-1,2-dioxolane - epoxidation

References and Notes

• 1 Jones CW. Application of Hydrogen Peroxide and Derivatives   RSC; Cambridge: 1999. 
• 2 Sanchez DAG. Synlett  2008,  1101 
• 3 Grigoropoulou G. Clark JH. Elings JA. Green Chem.  2003,  5:  1 
• 4 Miranda Les P. Lubell DW. Halkes MK. Groth T. Grotli M. Rademann J. Gotferdsen CH. Meldal M.
  J. Comb. Chem.  2002,  4:  523 
• 5 Cole DC. Stock JR. Kappel JA. Bioorg. Med. Chem. Lett.  2002,  12:  1791 
• 6 For reviews, see: Nardello V. Aubry J.-M. De Vos DE. Neumann R. Adam W. Zhang R. ten Elshof JE. Witte PT. Alsters PL. J. Mol. Catal. A.: Chem.  2006,  251:  185 
• 7 Lane BS. Burgess K. Chem. Rev.  2003,  103:  2457 
• 8 Benjamin S. Lane SS. Kevin B. Chem. Rev.  2003,  103:  2457 
• 9 For a review, see: Kratz T. Zeiss W. In Peroxide Chemistry   Adam W. Wiley-VCH; Weinheim: 2000.  p.41-59  
• 10 For leading examples, see: Iskara J. Bonnet-Delpon D. Begue JP. Tetrahedron Lett.  2003,  44:  6309 
• 11 Tsuchiya K. Hamada Y. Masuyama A. Nojima M. McCullough KJ. Kim H.-S. Shibata Y. Wataya Y. Tetrahedron Lett.  1999,  40:  4077 
• 12 Selvam JJP. Suresh V. Rajesh K. Rabu DC. Suryakiran N. Venkateswalu Y. Tetrahedron Lett.  2008,  49:  3463 
• 13 Zheng Y.-J. Bruice TC. Bioorg. Chem.  1997,  25:  331 
• 14 Merényi G. Lind J. J. Am. Chem. Soc.  1991,  113:  3146 
• 15 Miller AE. Bischoff JJ. Bizub C. Luminoso P. Smiley S. J. Am. Chem. Soc.  1986,  108:  7773 
• 16 Doerge DR. Corbett MD. Mol. Pharmacol.  1984,  26:  348 
• 17 Oae S. Asada K. Yoshimura T. Tetrahedron Lett.  1983,  24:  1265 
• 18 Bruice TC. Noar JB. Ball SS. Venkataram UV.
  J. Am. Chem. Soc.  1983,  105:  2452 
• 19 Ball S. Bruice TC. J. Am. Chem. Soc.  1981,  103:  5494 ; and references cited therein
• 20 Kośnik W. Bocian W. Kozerski L. Tvaroška I. Chmielewski M. Chem. Eur. J.  2008,  14:  6087 
• 21 Azarifar D. Khosravi K. Eur. J. Chem.  2010,  15 
• 22 Bez G. Zhao C.-G. Tetrahedron Lett.  2003,  44:  7403 
• 23 Adam W. Saha-Möller CR. Zhao C.-G. Tetrahedron: Asymmetry  1999,  10:  2749 
• 24 Adam W. Saha-Möller CR. Ganeshpure PA. Chem. Rev.  2001,  101:  3499 
• 25 Udin AK. Aziridines and Epoxides in Organic Synthesis   Wiley-VCH; Weinheim: 2006. 
• 26 Rudolph J. Reddy KL. Chiang JP. Sharpless KB.
  J. Am. Chem. Soc.  1997,  119:  6189 
• 27 Li Z. Zhou Z. Li K. Wang L. Zhou Q. Tang C. Tetrahedron Lett.  2002,  43:  7609 
• 28 De Vos DE. Sels BF. Reynaers M. Rao YVS. Jacobs PA. Tetrahedron Lett.  1998,  39:  3221 
• 29 Bonini C. Righi G. Tetrahedron  2002,  58:  4981 
• 30 Wong E. In Chemistry and Biochemistry of Plants Pigments   Goodwin TW. Academic; New York: 1976. 
• 31 Dhar DN. The Chemistry of Chalcones and Related Compounds   Wiley Interscience; New York: 1981. 
• 32 Bohm BA. In The Flavonoids: Advances in Research Since 1980   Harborne JB. Chapman and Hall; London: 1988. 
• 33 Roberts S. Skidmore J. Chem. Ber.  2002,  31 
• 34 Martinelli MJ. Peterson BC. Khau VV. Hutchison DR. Leana MR. Audia JE. Droste JJ. Wu YD. Houk KN. J. Org. Chem.  1986,  51:  3098 
• 35 Solladie GS. Hutt J. J. Org. Chem.  1987,  52:  3560 
• 36 Hoeger CA. Johnstone AD. Okamura WH. J. Am. Chem. Soc.  1987,  109:  4690 
• 37 Baures PW. Egglestone DS. Flisak JR. Gonbatz K. Lantos I. Mendelson W. Remich JJ. Tetrahedron Lett.  1990,  31:  6501 
• 38 Itsuno S. Sakaura M. Ito K. J. Org. Chem.  1990,  55:  6047 
• 39 Honma T. Nakajo N. Mizugaki T. Ebitani K. Kaneda K. Tetrahedron Lett.  2002,  43:  6229 
• 40 Lakouraj MM. Movassagh B. Bahrami K. Synth. Commun.  2001,  31:  1237 
• 41 Miyashita M. Suzuki T. Yoshkoshi A. Chem. Lett.  1987,  285 
• 42 Straub TS. Tetrahedron Lett.  1995,  36:  663 
• 43 Sharifi A. Bolourtchian M. Mohsenzadeh F. J. Chem. Res.  1998,  668 
• 44 Jakka K. Liu J. Zhao CG. Tetrahedron Lett.  2007,  48:  1395 
• 45 Bernini R. Mincione E. Coratti A. Fabrizi G. Battistuzzi G. Tetrahedron  2004,  60:  967 
• 46 Pluim H. Wynberg H. J. Org. Chem.  1980,  45:  2498 
• 47 Burke SD. Murtiashaw CW. Saunders JO. Oplinger JA. Dike MS. J. Am. Chem. Soc.  1984,  106:  4558 
• 48 Yadav VK. Kapoor KK. Tetrahedron Lett.  1994,  35:  9481 
• 49 Acene JL. Arjona O. Dellapradilla RF. Plumet J. Viso A. J. Org. Chem.  1994,  59:  6419 
• 50 Baggiolini EG. Iacobelli JA. Hennessy BM. Batcho AD. Sereno JF. Uskokovic MR. J. Org. Chem.  1986,  51:  3098 
• 51 Lv J. Wang X. Liu J. Zhang L. Wang Y. Tetrahedron: Asymmetry  2006,  17:  330 
• 52 Kienle M. Argyarakis W. Baro A. Laschat S. Tetrahedron Lett.  2008,  49:  1971 
• 53 Azarifar D. Khosravi K. Soleimani F. Synthesis  2009,  2553 
• 54 Azarifar D. Khosravi K. Soleimani F. Molecules  2010,  15:  1433 
• 56 Zolfigol MA. Chehardoli G. Shiri M. React. Funct. Polym.  2007,  67:  723 

55

Caution
Although we did not encounter any problem with trans-3,5-dihydroperoxy-3,5-dimethyl-1,2 dioxolane (1), it is potentially explosive and should be handled with precautions; all reactions should be carried out behind a safety shield inside a fume hood and transition-metal salts or heating should be avoided.
Preparation of trans-3,5-Dihydroperoxy-3,5-dimethyl-1,2-dioxolane (1) ^²¹
To a stirred solution of acetylacetone (100 mg, 1 mmol) in MeCN (5 mL) was added SnCl₂×2H₂O (45 mg, 0.2 mmol), and stirring of the reaction mixture was continued for 5 min at r.t. Then, aq 30% H₂O₂ (5 mmol) was added to the reaction mixture and was allowed to stir for 12 h at r.t. After completion of the reaction as monitored by TLC, H₂O (15 mL) was added, and the product was extracted into EtOAc (2 Ž 10 mL). The combined organic layer was dried over anhyd MgSO₄ and evaporated under reduced pressure to give almost pure white crystalline product 1, in 85% yield (140 mg); mp 98-100 ˚C.
General Experimental Procedure To a mixture of trans-chalcone 2 (1.0 mmol) and trans-3,5-dihydroperoxy-3,5-dimethyl-1,2-dioxolane (1, 166 mg, 1 mmol) in DME (5 mL) was added 1.0 M aq KOH solution (1 mL). The reaction mixture was stirred at r.t. for 2 h. After completion of the reaction (TLC), the remaining peroxide was neutralized with aq Na₂SO₃ solution. The resulting mixture was diluted with Et₂O (15 mL) and washed with H₂O (10 mL). The organic layer was dried over anhyd MgSO₄, and then the solvent was removed under reduced pressure. The remaining crude product was purified by column chromatography (eluent hexane-EtOAc, 90:10) to provide pure epoxide 3 (Table 2). Physical and spectroscopic (IR, ^¹H NMR, and ^¹³C NMR) data for some selected compounds are given.
Compound 3g: white solid, mp 72-74 ˚C. ^¹H NMR (90 MHz, CDCl₃-TMS): δ = 7.10-8.00 (m, 8 H), 4.42 (d, 1 H), 4.03 (d, 1 H), 2.21 (s, 3 H). ^¹³C NMR (22.5 MHz, CDCl₃): δ = 195.1, 143.6, 136.0, 134.2, 129.0, 125.8, 70.3, 63.0, 25.5. IR (KBr): ν_max = 3069, 1677, 1605, 1415, 1236, 1162, 1012, 899, 766, 674 cm^-¹. Anal. Calcd (%) for C₁₆H₁₃ClO₂: C, 70.59; H, 4.78. Found: C, 70.52.14; H, 4.74. MS (EI):
m/z = 272 [M⁺].
Compound 3m: white solid, mp 78-80 ˚C. ^¹H NMR (90 MHz, CDCl₃-TMS): δ = 7.20-8.00 (m, 9 H), 4.36 (d, 1 H), 4.04 (d, 1 H), 2.37 (s, 3 H). ^¹³C NMR (22.5 MHz, CDCl₃): δ = 193.5, 155.0, 150.8, 142.4, 136.0, 131.05, 129.7, 126.0, 114.4, 72.5, 62.1, 55.6. IR (KBr): ν_max = 3020, 2983, 2867, 1667, 1583, 1502, 1455, 1305, 1279, 1165, 1140, 1054, 827, 731, 693 cm^-¹. Anal. Calcd (%) for C₁₆H₁₄O₂: C, 80.67; H, 5.88. Found: C, 80.63; H, 5.82. MS (EI): m/z = 238 [M⁺].
Compound 3o: white solid, mp 146-148 ˚C. ^¹H NMR (90 MHz, CDCl₃-TMS): δ = 7.50-8.30 (m, 9 H), 4.30 (d, 1 H), 4.18 (d, 1 H). ^¹³C NMR (22.5 MHz, CDCl₃): δ = 192.2, 153.8, 143.5, 140, 138.0, 130.7, 128.5, 125.0, 119.6, 70.1, 62.5. IR (KBr): ν_max = 3063, 1659, 1594, 1493, 1395, 1333, 1128, 824, 742, 687 cm^-¹. Anal. Calcd (%) for C₁₅H₁₁NO₄: C, 66.91; H, 4.09; N, 5.20. Found: C, 66.82; H, 4.02; N, 5.15. MS (EI): m/z = 269 [M⁺].
Compound 3p: white solid, mp 117-119 ˚C. ^¹H NMR (90 MHz, CDCl₃-TMS): δ = 7.50-8.03 (m, 9 H), 4.32 (d, 1 H), 4.22 (d, 1 H). ^¹³C NMR (22.5 MHz, CDCl₃): δ = 198.2, 153.8, 145.7, 137.4, 134.3, 133.0, 129.5, 126.8, 121.7, 71.1, 62.0. IR (KBr): ν_max = 3061, 3025, 2923, 1797, 1595, 1495, 1395, 1337, 1139, 848, 747, 690 cm^-¹. Anal. Calcd (%) for C₁₅H₁₁NO₄: C, 66.91; H, 4.09; N, 5.20. Found: C, 66.85; H, 4.04; N, 5.17. MS (EI): m/z = 269 [M⁺].