Cationic Iron(III) Porphyrin Catalyzed Dehydrative Friedel–Crafts Reaction of Alcohols with Arenes

Abstract

Alcohols react with arenes in the presence of cationic iron(III) porphyrin catalyst. The reaction involves the formation of the C–C bond via dehydration, which is formal Lewis acid catalyzed Friedel–Crafts reaction.

Key words

alcohols - arenes - coupling - iron - porphyrins

• References and Notes


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• 7 General Procedure for the Dehydrative Friedel–Crafts Reaction of Alcohols with Arenes To a screw-cap vial was added [Fe(TPP)][SbF₆] (0.02 mmol, 18 mg), followed by the alcohol (0.4 mmol), the arene (2 mmol), and dry 1,2-DCE (1.0 mL) in a dry box. The vial was sealed and stirred at 80 °C for 5 h. The reaction mixture was diluted with hexane–EtOAc (10:1), passed through a short silica gel pad and washed with hexane–EtOAc (1:1), concentrated in vacuo. The crude product was purified by flash column chromatography using SiO₂ (hexane–EtOAc). Selected Data for Compound 3aa Yield: 72%; colorless oil. TLC: R_f  = 0.62 (hexane–toluene, 2:1). ¹H NMR (500 MHz, CDCl₃): δ = 7.36 (d, J = 7.5 Hz, 2 H), 7.31–7.28 (m, 2 H), 7.22–7.16 (m, 3 H), 6.88–6.86 (m, 1 H), 6.44 (d, J = 16.0 Hz, 1 H), 6.38–6.32 (m, 1 H), 3.81 (s, 3 H), 3.50 (d, J = 6.5 Hz, 3 H). ¹³C NMR (125 MHz, CDCl₃): δ = 158.1, 137.5, 132.2, 130.7, 129.7, 129.6, 128.5, 127.0, 126.1, 113.9, 55.3, 38.4. IR (neat): 3025, 1511, 1246, 1175, 1035, 966, 827, 729, 692 cm^–1. MS: m/z (%) = 224/25 (100/17) [M⁺]. HRMS (APCI): m/z [M + H]⁺ calcd for C₁₆H₁₆O: 225.1274; found: 225.1269.