Synlett 2013; 24(11): 1377-1382
DOI: 10.1055/s-0033-1338947
letter
© Georg Thieme Verlag Stuttgart · New York

Oxidative Cleavage of C=C Bonds with Singlet Molecular Oxygen Generated from Monoacetylated Bishydroperoxides

Davood Azarifar*
Faculty of Chemistry, Bu-Ali Sina University, 65178 Hamedan, Iran   Fax: +98(811)8257407   Email: azarifar@basu.ac.ir
,
Zohreh Najminejad
Faculty of Chemistry, Bu-Ali Sina University, 65178 Hamedan, Iran   Fax: +98(811)8257407   Email: azarifar@basu.ac.ir
› Author Affiliations
Further Information

Publication History

Received: 21 February 2013

Accepted after revision: 18 April 2013

Publication Date:
10 June 2013 (online)


Abstract

The oxidative cleavage of C=C bonds adjacent to aryl and alkyl moieties was efficiently achieved with monoacetylated bishydroperoxides. The main active oxidant used in this reaction was singlet molecular oxygen, which was generated in situ from the base-mediated fragmentation of monoacetylated bishydroper­oxides. All the reactions proceeded smoothly at room temperature to furnish the respective carbonyl compounds in good yields within short reaction times.

 
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    Oxidant A:
    Yield: 84% (0.42 g); mp 38–40 °C; 1H NMR (200 MHz, CDCl3): δ = 9.43 (br s, 1 H, OOH), 2.67 (s, 2 H, 4-CH 2), 2.17 (s, 3 H, Ac), 1.61 (s, 3 H, CH3), 1.59 (s, 3 H, CH3). 13C NMR (50 MHz, D2O): δ = 171.7 (CO), 112.7 (C), 120.9 (C), 50.7, 17.6, 16.5. IR (KBr): 3389, 2869, 1750, 1433, 1380, 1333, 1173, 848, 790 cm–1. Anal. Calcd for C7H12O7: C, 40.38; H, 5.77. Found: C, 40.46; H, 5.72. Oxidant B: Yield: 80% (0.47 g); mp 35–37 °C; 1H NMR (200 MHz, CDCl3): δ = 10.22 (s, 1 H, OOH), 2.17 (s, 3 H, Ac), 2.00 (m, 4 H, CH2), 1.76 (m, 4 H, CH2), 1.57 (m, 1 H, CH), 0.88 (s, 9 H, CH3). 13C NMR (50 MHz, D2O): δ = 172.6 (CO), 120.9 (C-1), 47.3, 34.6, 34.5, 31.6, 27.3, 17.6. IR (KBr): 3240, 2869, 1750, 1365, 1186, 1070, 960 cm–1. Anal. Calcd for C12H22O5: C, 58.53; H, 8.94. Found: C, 58.62; H, 8.85. Oxidative Cleavage of Alkenes to the Respective Carbonyl Compounds; Typical Procedure: To a mixture of aryl alkene (1 mmol) and monoacetylated bishydroperoxide A or B (1 mmol) in MeCN (5 mL) was added 1.0 M aq n-Bu4NF (2 mL). The mixture was stirred at room temperature for an appropriate time (Table 3). After completion of the reaction as monitored by TLC, the remaining peroxide was neutralized by the addition of aq Na2SO3. The resulting mixture was diluted with Et2O (15 mL) and washed with H2O (10 mL), then the organic layer was dried over anhydrous MgSO4, filtered, and evaporated under reduced pressure. Purification of the crude solid residue by column chromatography gave the pure products. All the products produced from these reactions are known compounds and were characterized on the basis of their physical and spectral (IR, 1H and 13C NMR) data, which were in accord with those reported.
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