Phosphomolybdic Acid Catalyzed Synthesis of 1,2,4,5-Tetraoxanes

Abstract

1,1-Dihydroperoxides were converted into 1,2,4,5-tetraoxanes through condensation with the corresponding ketones in 36-91% yields using phosphomolybdic acid as the catalyst and anhydrous MgSO₄ as the water scavenger.

Key words

phosphomolybdic acid - catalysis - cyclic condensation - 1,2,4,5-tetraoxanes - peroxide

References and Notes

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21

Representative Procedure for the Preparation of Adamantane-2-spiro-3′-1′,2′,4′,5′-tetraoxane-6′-spiro-4′′- tert -butyl-1′′-cyclohexane (6)
A mixture of 4h (88 mg, 0.59 mmol, 1.5 equiv), PMA (7 mg, 3.9 µmol, 1 mol%), and anhyd MgSO₄ (71 mg, 0.59 mmol, 1.5 equiv) in CH₂Cl₂ (3 mL) was stirred for 20 min at r.t. To this solution was added 5c (80 mg, 0.39 mmol, 1.0 equiv) in CH₂Cl₂ (3 mL) in 15 min. The mixture was stirred at r.t. and monitored by TLC. When 5c was consumed completely, H₂O (10 mL) was added. The organic layer was separated, and the aqueous layer was extracted with CH₂Cl₂ (3 × 10 mL). The combined organic phase was dried by anhyd Na₂SO₄ and concentrated in vacuo. The residue was purified by silica gel column chromatograph (PE-EtOAc = 400:1) to afford 6 (58 mg, yield 44%) as white solid; mp 136-138 ˚C (lit.^¹4 134-136 ˚C). R _f  = 0.79 (PE-EtOAc, 50:1). ^¹H NMR (400 MHz, CDCl₃): δ = 3.17 (s, 2 H), 1.97 (s, 4 H), 1.86 (s, 2 H), 1.82-1.51 (m, 9 H), 1.50-1.35 (m, 2 H), 1.35-1.15
(s, 3 H), 1.08 (m, 1 H), 0.86 (s, 9 H). ^¹³C NMR (400 MHz, CDCl₃): δ = 110.4, 108.2, 47.6, 37.1, 34.5, 33.3, 32.6, 32.3, 29.8, 27.8, 27.2, 23.2.^¹4