Bismuth Triflate-Catalyzed Fries Rearrangement of Aryl Acetates

Abstract

Bismuth triflate was found to be an efficient catalyst in the Fries rearrangement of phenyl or 1-naphthyl acetates. Both reactions proceeded smoothly with a catalytic amount of bismuth triflate (10 mol%) to afford the corresponding hydroxyaryl ketone in moderate to good yields in most cases.

Fries rearrangement - bismuth(III) - Lewis acid - phenol - hydroxyaryl ketone - green chemistry

References

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Bi(OTf)₃ has been prepared from Bi₂O₃ according to ref. [11a]

<A NAME="RS07104ST-12">12</A>

Interestingly, a metal triflate screening for the catalytic Fries rearrangement was independantly studied by C. Le Roux. [2d] He showed that Bi(OTf)₃ was slightly less efficient than Sc(OTf)₃ but could get a synergistic effect using Bi(OTf)₃ + MeSO₃H.

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Nitroethane is a good alternative to potentially explosive nitromethane in the presence of a Lewis acid.

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<A NAME="RS07104ST-16">16</A>

A representative procedure for the Bi(OTf)₃-catalyzed Fries rearrangement is at follows: To a solution of acetate 1 or 4 (1.00 mmol) in the solvent (2 mL) was added Bi(OTf)₃·4H₂O (0.10 mmol). The mixture was magnetically stirred and heated at 110 °C for 3-33 h. The reaction mixture was quenched by the addition of H₂O, extracted with Et₂O, dried over anhyd Na₂SO₄, filtered, and concentrated under vacuum (rotary evaporator). The residue was purified by column chromatography on silica gel using hexanes-EtOAc (99:1-90:10) as eluent. All the compounds were characterized by IR and ¹H NMR spectroscopy, and accord exactly with those that have been previously reported in the literature.