Chemoselective Epoxidation of Electron Deficient Enones with Iodosylbenzene

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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• 17 Compound 12: ¹H NMR (400 MHz, CDCl₃): δ = 1.73-1.79 (m, 1 H), 1.88-1.97 (m, 1 H), 2.05-2.14 (m, 1 H), 2.19-2.27 (m, 1 H), 2.34-2.40 (m, 1 H), 2.61-2.68 (m, 1 H), 4.04-4.06 (m, 1 H). ¹³C NMR (400 MHz, CDCl₃): δ = 16.7, 22.6, 35.8, 51.6, 63.1, 114.1, 196.8
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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] ).