Copper-Catalyzed Alkenylation of Alcohols with β-Nitrostyrenes via a Radical Addition–Elimination Process

Abstract

A new method for the preparation of allylic alcohol derivatives has been developed via a radical mechanism using DTBP as the radical initiator promoted by copper salt. The C(sp³)–H bond in various alcohols, toluene derivatives, and alkanes were successfully converted into C–C bonds to yield the desired products in moderate to good yields.

Key words

(E)-β-nitrostyrenes - alkenylation - alcohols - free-radical - C(sp³)–H bonds

• References and Notes

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• 14 Typical Procedure To a Schlenk tube equipped with a magnetic stir bar were added, under argon, β-nitrostyrene (0.5 mmol) and Cu(OAc)₂ (0.01 mmol). Under argon, isopropanol (3.0 mL) and di-tert-butyl peroxide (DTBP, 1 mmol) were added. The resulting reaction mixture was kept stirring at the required temperature for 2–6 h. After the required reaction time, the mixture was cooled down to r.t. Evaporation of the solvent followed by purification by flash chromatography (PE–EtOAc = 5:1) afforded the corresponding product 3aa in 83% yield. (E)-2-Methyl-4-phenylbut-3-en-2-ol (3aa) Colorless oil. ¹H NMR (300 MHz, CDCl₃): δ = 7.39 (dd, J = 8.2, 1.3 Hz, 2 H), 7.35–7.28 (m, 2 H), 7.25 (dd, J = 5.9, 4.2 Hz, 1 H), 6.60 (d, J = 16.1 Hz, 1 H), 6.36 (d, J = 16.1 Hz, 1 H), 1.64 (s, 1 H), 1.43 (s, 6 H). ¹³C NMR (75 MHz, CDCl₃): δ = 137.59, 131.75, 128.60, 127.47, 126.46, 117.31, 71.10, 29.95. HRMS (TOF, EI⁺): m/z calcd for C₁₁H₁₄O: 162.1045; found: 162.1044.