Fries rearrangement
Introducion
The Fries rearrangement reaction is the synthesis of o- or para-acyl phenols from phenolic esters catalyzed by Lewis or Brønsted acids (e.g., HF, AlCl3, BF3, TiCl4, or SnCl4).
1 The Fries rearrangement reaction was first reported by the German chemist Karl Theophil Fries, after whom it was named, and is one of the most important human reactions.
Figure 1. Fries rearrangement reaction
Fries rearrangement can also be carried out without a catalyst, but requires the presence of UV light. The product is still an ortho- or para-hydroxyaryl ketone. This type of Fries rearrangement is called "photo-Fries rearrangement". The yield of photo-Fries rearrangement is very low and is rarely used in synthesis. It is still possible to perform photo-Fries rearrangement when the benzene ring is not sufficiently interpositioned.1
The thia-Fries rearrangement refers to the rearrangement of aryl trifluoromethanesulfonates into trifluoromethanesulfonyl phenols catalyzed by aluminum chloride in a dichloromethane system.2
The anionic phosphoric acid Fries rearrangement generates phenols containing an adjacent carbon-phosphorus bond, which can rearrange the aryl phosphate ester [ArOP(=O)(OR)2] to o-hydroxyaryl phosphonate [o-HO-Ar-P(=O)(OR)2]. 3
Application
The Fries rearrangements are currently used in the following applications:
nApplied to the synthesis conditions of benzoic acid phenyl ester rearrangement reaction to produce o-hydroxybenzophenone and para-hydroxybenzophenone using ionic melt [1-butyl-3-methylimidazolium chloroaluminate ([BMIm]Cl-xAlCl3)] as solvent and Lewis acid as catalyst. 4
Figure 2.Para hydroxybenzophenone
nSynthesis of pharmaceutical intermediates o-hydroxyacetophenone and p-hydroxyacetophenone. o-hydroxyacetophenone and p-hydroxyacetophenone are one of the important raw materials for organic synthesis and are widely used intermediates in the pharmaceutical field. And o-hydroxyacetophenone and p-hydroxyacetophenone are mainly synthesized by Fries rearrangement reaction of phenyl acetate. 5
nThe synthesis of vitamin E (α-tocopherol). 6
nSynthesis of o-acyl hydroxyl [2.2] p-cyclopentane using Fries rearrangement with direct regioselective acylation reaction catalyzed by TiCl4. 7
nSynthesis of agrochemical intermediates o-hydroxybutyrophenone and p-hydroxybutyrophenone. o/p-hydroxybutyrophenone,a mixture of o-hydroxybutyrophenone and p-hydroxybutyrophenone, is a new agrofungicide. Currently, o/p-hydroxybutyrophenone is often prepared from phenyl butyrate by Friesc rearrangement.8
nAcyl naphthalene was synthesized into hydroxynaphthone by Fries rearrangement catalyzed by scandium trifluoromethanesulfonate.9
nSynthesis of 5-, 6-, and 7-substituted benzodipyran-4-ones from 3-methyl-2-butenoic acid aryl esters by photo-Fries rearrangement and base-catalyzed intramolecular oxa-Michael addition reactions using a photochemical one-pot method. 10
The above synthesis scheme:
Figure 3.Oxa Michael Addition Reaction
Research Progress
nA related study on thiourea-Fries rearrangement under solvent-free, microwave-mediated heating conditions. 8
nPhoto-responsive liquid crystal polymer films undergo photo-Fries rearrangement with axial selection and exhibit photo-induced optical anisotropy when exposed to linearly polarized ultraviolet light (LPUV).1
nFries rearrangement is a crucial step in the synthesis of the unsaturated putative precursor muricadienin in trans- and cis-solamin biosynthesis. 10
nChiral ferrocenyl phosphates are synthesized by anionic phosphoric acid-Fries rearrangement containing diastereoisomers of 1,2-P,O-phosphate, which will then be further converted to enantiomerically pure phospholides. 13
nA study on the liquid-phase-Fries rearrangement reaction of aryl esters catalyzed by heteropolyacid H3PW12O40 (PW) loaded on silica or its salt Cs2.5H0.5PW12O40 (CsPW) 14.
nAnionic phosphoric acid-Fries has been successfully applied in studies related to ferrocene chemistry. 15
nFries rearrangement with 2,6-dimethoxyquinone has been used for the synthesis of antiviral flavonoid lead compounds. 16
Figure 4.Dimethoxyquinone
nHeteropolyacid H3PW12O40 has been applied to the Fries rearrangement of phenyl acetate as a high performance and environmentally friendly catalyst.
Figure 5.Phenyl Acetate
Reference:
1.Bansal R K. 1996. Synthetic Approaches in Organic Chemistry. Jones & Bartlett Learning.
2.Chen X, Tordeux M, Desmurs J, Wakselman C. 2003. Thia-Fries rearrangement of aryl triflinates to trifluoromethanesulfinylphenols. Journal of Fluorine Chemistry. 123(1):51-56.
https://doi.org/10.1016/s0022-1139(03)00106-43.Taylor C, Watson A. 2004. The Anionic Phospho-Fries Rearrangement. COC. 8(7):623-636.
https://doi.org/10.2174/13852720433707174.Harjani JR, Nara SJ, Salunkhe MM. 2001. Fries rearrangement in ionic melts. Tetrahedron Letters. 42(10):1979-1981.
https://doi.org/10.1016/s0040-4039(01)00029-65.Jayat F, Picot MJS, Guisnet M. 1996. Solvent effects in liquid phase Fries rearrangement of phenyl acetate over a HBEA zeolite. Catal Lett. 41(3-4):181-187.
https://doi.org/10.1007/bf008114886.Termath AO, Velder J, Stemmler RT, Netscher T, Bonrath W, Schmalz H. 2014. Total Synthesis of (2RS)-?-Tocopherol through Ni-Catalyzed 1,4-Addition to a Chromenone Intermediate. Eur. J. Org.Chem.. 2014(16):3337-3340.
https://doi.org/10.1002/ejoc.2014022407.Rozenberg V, Danilova T, Sergeeva E, Vorontsov E, Starikova Z, Lysenko K, Belokon .Y.Eur J. 2000. Org.Chem. 193295.
8.Moghaddam FM, Dakamin MG. 2000. Thia-Fries rearrangement of aryl sulfonates in dry media under microwave activation. Tetrahedron Letters. 41(18):3479-3481.
https://doi.org/10.1016/s0040-4039(00)00402-09.Kobayashi S, Moriwaki M, Hachiya I. 1995. The catalytic Fries rearrangement of acyloxy naphthalenes using scandium trifluoromethanesulfonate as a catalyst. J. Chem. Soc., Chem. Commun..(15):1527.
https://doi.org/10.1039/c3995000152710.Iguchi D, Erra-Balsells R, Bonesi SM. 2014. Expeditious photochemical reaction toward the preparation of substituted chroman-4-ones. Tetrahedron Letters. 55(33):4653-4656.
https://doi.org/10.1016/j.tetlet.2014.06.08111.Uraoka H, Kondo M, Kawatsuki N. 2014. Influence of End Groups in Photoinduced Reorientation of Liquid Crystalline Polymer Films Based on Axis-Selective Photo-Fries Rearrangement. Molecular Crystals and Liquid Crystals. 601(1):79-87.
https://doi.org/10.1080/15421406.2014.94050812.Adrian J, Stark CBW. 2014. Total Synthesis of Muricadienin, the Putative Key Precursor in the Solamin Biosynthesis. Org.Lett.. 16(22):5886-5889.
https://doi.org/10.1021/ol502849y13.Korb M, Lang H. 2014. Planar Chirality from the Chiral Pool: Diastereoselective Anionic Phospho-Fries Rearrangements at Ferrocene. Organometallics. 33(22):6643-6659.
https://doi.org/10.1021/om500953c14.Kozhevnikova E. 2004. Fries rearrangement of aryl esters catalysed by heteropoly acid: catalyst regeneration and reuse. Applied Catalysis A: General. 260(1):25-34.
https://doi.org/10.1016/j.apcata.2003.10.00815.Korb M, Schaarschmidt D, Lang H. 2014. Anionic Phospho-Fries Rearrangement at Ferrocene: One-Pot Approach to P,O-Substituted Ferrocenes. Organometallics. 33(8):2099-2108.
https://doi.org/10.1021/om500282716.Martin-Benlloch X, Elhabiri M, Lanfranchi DA, Davioud-Charvet E. 2014. A Practical and Economical High-Yielding, Six-Step Sequence Synthesis of a Flavone: Application to the Multigram-Scale Synthesis of Ladanein. Org.Process Res. Dev.. 18(5):613-617.
https://doi.org/10.1021/op400364217.Kozhevnikova EF, Derouane EG, Kozhevnikov IV. 2002. Heteropoly acid as a novel efficient catalyst for Fries rearrangement. Chem. Commun..(11):1178-1179.
https://doi.org/10.1039/b202148j