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DOI: 10.1055/s-2004-836025
Bismuth Triflate-Catalyzed Fries Rearrangement of Aryl Acetates
Publication History
Publication Date:
25 November 2004 (online)
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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
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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
References
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.
13Nitroethane is a good alternative to potentially explosive nitromethane in the presence of a Lewis acid.
16A 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.