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.

Key words

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

References

• 1a Martin R. Org. Prep. Proced. Int.  1992,  24:  369 
• 1b Crouse DJ. Hurlbut SL. Wheeler DMS. J. Org. Chem.  1981,  46:  374 
• 2a Kobayashi S. Moriwaki M. Hachiya I. Bull. Chem. Soc. Jpn.  1997,  70:  267 
• 2b Kobayashi S. Moriwaki M. Hachiya I. Tetrahedron Lett.  1996,  37:  2053 
• 2c Kobayashi S. Moriwaki M. Hachiya I. J. Chem. Soc., Chem. Commun.  1995,  1527 
• 2d Mouhtady O. Gaspard-Iloughmane H. Roques N. Le Roux C. Tetrahedron Lett.  2003,  44:  6379 ; and erratum: Tetrahedron Lett. 2003, 44, 8037
• 3a Organobismuth Chemistry   Suzuki H. Matano Y. Elsevier; Amsterdam: 2001. 
• 3b Gaspard-Iloughmane H. Le Roux C. Eur. J. Org. Chem.  2004,  2517 
• 3c Leonard NM. Wieland LC. Mohan RS. Tetrahedron  2002,  58:  8373 
• 4a Ollevier T. Lavie-Compin G. Tetrahedron Lett.  2004,  45:  49 
• 4b Ollevier T. Lavie-Compin G. Tetrahedron Lett.  2002,  43:  7891 
• 5 Ollevier T. Ba T. Tetrahedron Lett.  2003,  44:  9003 
• 6a Le Roux C. Ciliberti L. Laurent-Robert H. Laporterie A. Dubac J. Synlett  1998,  1249 
• 6b Le Roux C. Gaspard-Iloughmane H. Dubac J. Jaud J. Vignaux P. J. Org. Chem.  1993,  58:  1835 
• 6c Wada M. Takeichi M. Matsumoto T. Bull. Chem. Soc. Jpn.  1991,  64:  990 
• 6d Ohki H. Wada M. Akiba K. Tetrahedron Lett.  1988,  29:  4719 
• 7a Leonard NM. Oswald MC. Freiberg DA. Nattier BA. Smith RC. Mohan RS. J. Org. Chem.  2002,  67:  5202 
• 7b Carrigan MD. Sarapa D. Smith RC. Wieland LC. Mohan RS. J. Org. Chem.  2002,  67:  1027 
• 8a For a review on bismuth chloride and bismuth triflate in acylation reactions: Le Roux C. Dubac J. Synlett  2002,  181 
• 8b Desmurs JR. Labrouillère M. Le Roux C. Gaspard H. Laporterie A. Dubac J. Tetrahedron Lett.  1997,  38:  8871 
• 8c Répichet S. Le Roux C. Dubac J. Desmurs JR. Eur. J. Org. Chem.  1998,  2743 
• 8d Laporte C. Marquie J. Laporterie A. Desmurs JR. Dubac J. C. R. Acad. Sci. II C  1999,  2:  455 
• 9a Garrigues B. Oussaid A. J. Organomet. Chem.  1999,  585:  253 
• 9b Laurent-Robert H. Garrigues B. Dubac J. Synlett  2000,  1160 
• 10a Leroy B. Markó IE. Org. Lett.  2002,  4:  47 
• 10b Leroy B. Markó IE. Tetrahedron Lett.  2001,  42:  8685 
• 11a Répichet S. Zwick A. Vendier L. Le Roux C. Dubac J. Tetrahedron Lett.  2002,  43:  993 
• 11b Labrouillère M. Le Roux C. Gaspard H. Laporterie A. Dubac J. Desmurs JR. Tetrahedron Lett.  1999,  40:  285 
• 11c Peyronneau M. Arrondo C. Vendier L. Roques N. Le Roux C. J. Mol. Catal. A: Chem.  2004,  211:  89 
• 11d

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

• 14 Kobayashi S. Moriwaki M. Hachiya I. Synlett  1995,  1153 
• 15a Orita A. Tanahashi C. Kakuda A. Otera J. J. Org. Chem.  2001,  66:  8926 
• 15b Orita A. Tanahashi C. Kakuda A. Otera J. Angew. Chem. Int. Ed.  2000,  39:  2877 

12

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.

13

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

16

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.