Substrate-Controlled Regioselective Iodooxygenation of Olefins

Abstract

An unexpected regioselective I₂/TBHP-mediated 1,2-iodo­oxygenation of alkenes with N-hydroxylamines is described. The reaction proceeds through a radical coupling mechanism or a iodonium mechanism, which is controlled by the structures of both N-hydroxylamines and alkenes, to form vicinal iodo-substituted N-alkoxyamines regioselectively. Both the iodo and alkoxyamine group of the resulting products offer rich possibilities of synthetic manipulations.

Key words

iodooxygenation - regioselectivity - alkenes - N-hydroxyphthalimide - 1-hydroxybenzotriazole

• References and Notes

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• 9 General Procedure for the Synthesis of Compounds 2Alkenes (0.3 mmol) and TBHP (0.6 mmol) was added to a solution of 1-hydroxybenzotriazole (0.36 mmol) and iodide (0.15 mmol) in 2 mL of DCE. After the reaction mixture was stirred at 40 °C for 2 h, the solvent was removed under reduced pressure, and the residual was treated with silica gel chromatography to give compounds 2.1-(2-Iodo-2-phenylethoxy)-1H-benzo[d][1,2,3]triazole (2a)Colorless oil. ¹H NMR(500 MHz, CDCl₃): δ = 7.93 (d, J = 8.3 Hz, 1 H), 7.39–7.32 (m, 6 H), 7.29 (m, 2 H), 5.69 (t, J = 7.0Hz, 1 H), 3.93 (dd, J = 10.8, 7.1 Hz, 1 H), 3.71 (dd, J = 10.8, 7.0 Hz, 1 H). ¹³C NMR (125 MHz, CDCl₃): δ = 143.12, 135.4, 130.1, 128.8, 127.90,127.87, 127.5, 124.4, 120.0, 108.8, 91.8, 2.9. HRMS (ESI): m/z calcd for C₁₄H₁₃IN₃O [M + H⁺]: 366.0098; found: 366.0096.
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