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DOI: 10.1055/s-0031-1289864
Phosphomolybdic Acid Catalyzed Synthesis of 1,2,4,5-Tetraoxanes
Publikationsverlauf
Publikationsdatum:
09. November 2011 (online)
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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
- Supporting Information for this article is available online:
- Supporting Information
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References and Notes
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