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Synlett 2004(13): 2403-2405  
DOI: 10.1055/s-2004-832814
LETTER
© Georg Thieme Verlag Stuttgart · New York

Chemoselective Epoxidation of Electron Deficient Enones with Iodosylbenzene

Kevin M. McQuaid, Thomas R. R. Pettus*
Department of Chemistry and Biochemistry, University of California at Santa Barbara, Santa Barbara, CA 93106-9510, USA
Fax: 805-893-5690; e-Mail: pettus@chem.ucsb;
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Publication History

Received 13 May 2004
Publication Date:
08 September 2004 (online)

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Abstract

The epoxidation of electron deficient olefins is demonstrated with PhIO and an assortment of enones.

Key words

enone epoxidation - iodosylbenzene - enones

    References

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  • 19b

    Compound 14: IR (CH2Cl2): 3061, 3007, 2935, 1797, 1769, 1408, 1382, 1334, 1275, 1265, 1257, 1223, 1200, 1169, 1128, 1109, 1043, 1022, 985, 916, 908 cm-1. 1H NMR (400 MHz, CDCl3): δ = 1.60 (d, 1 H, J = 5.3 Hz), 1.84 (s, 3 H) 1.85 (s, 3 H), 3.76 (q, 1 H, J = 5.3 Hz). 13C NMR (400 MHz, CDCl3): δ = 12.8, 27.8, 28.2, 55.6, 64.7, 105.9, 161.9, 163.7. ES-MS: found [M + Na]+ 209.0420.
4

It is reported to explode at 210 °C. We, however, find that 3 g of PhIO can explode upon drying over toluene (110 °C, 0.1 torr), reducing a drying pistol to dust.

13

Compound 8: 1H NMR (400 MHz, CDCl3): δ = 3.60 (m, 1 H), 2.59 (m, 1 H), 2.35 (m, 1 H), 2.26 (s, 3 H), 2.16 (m, 1 H), 1.86 (m, 1 H), 1.76 (m, 1 H). We believe that byproduct 17 arises upon bifurcation of the mechanism as shown below (Scheme [3] ).