Friedel-Crafts Acylation

This electrophilic aromatic substitution allows the synthesis of monoacylated products from the reaction between arenes and acyl chlorides or anhydrides. The products are deactivated, and do not undergo a second substitution. Normally, a stoichiometric amount of the Lewis acid catalyst is required, because both the substrate and the product form complexes.

The Friedel-Crafts Alkylation may give polyalkylated products, so the Friedel-Crafts Acylation is a valuable alternative. The acylated products may easily be converted to the corresponding alkanes via Clemmensen Reduction or Wolff-Kishner Reduction.

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Mechanism of the Friedel-Crafts Acylation

Recent Literature

Reactions on a Solid Surface. A Simple, Economical and Efficient Friedel-Crafts Acylation Reaction over Zinc Oxide (ZnO) as a New Catalyst
M. H. Sarvari, H. Sharghi, J. Org. Chem., 2004, 69, 6953-6956.

Mild, Efficient Friedel-Crafts Acylations from Carboxylic Acids Using Cyanuric Chloride and AlCl₃
C. O. Kangani, B. W. Day, Org. Lett., 2008, 10, 2645-2648.

"Greener" Friedel-Crafts Acylations: A Metal- and Halogen-Free Methodology
M. C. Wilkinson, Org. Lett., 2011, 13, 2232-2235.

Simple and Improved Procedure for the Regioselective Acylation of Aromatic Ethers with Carboxylic Acids on the Surface of Graphite in the Presence of Methanesulfonic Acid
M. H. Sarvari, H. Sharghi, Synthesis, 2004, 2165-2168.

An intermolecular Friedel-Crafts acylation in hexafluoro-2-propanol provides aryl and heteroaryl ketones at room temperature without any additional reagents.
R. H. Vekariya, J. Aubé, Org. Lett., 2016, 18, 3534-3537.

Zinc Mediated Friedel-Crafts Acylation in Solvent-Free Conditions under Microwave Irradiation
M. H. Sarvari, H. Sharghi, J. Org. Chem., 2004, 69, 6953-6956.

Aluminum dodecatungstophosphate (AlPW₁₂O₄₀) as a non-hygroscopic Lewis acid catalyst for the efficient Friedel-Crafts acylation of aromatic compounds under solvent-less conditions
H. Firouzabadi, N. Iranpoor, F. Nowrouzi, Tetrahedron, 2004, 60, 10843-10850.

Esters as Acylating Reagent in a Friedel-Crafts Reaction: Indium Tribromide Catalyzed Acylation of Arenes Using Dimethylchlorosilane
Y. Nishimoto, S. A. Babu, M. Yasuda, A. Baba, J. Org. Chem., 2008, 73, 9465-9468.

In(III)-Mediated Chemoselective Dehydrogenative Interaction of ClMe₂SiH with Carboxylic Acids: Direct Chemo- and Regioselective Friedel-Crafts Acylation of Aromatic Ethers
S. A. Babu, M. Yasuda, A. Baba, Org. Lett., 2007, 9, 405-408.

Unsymmetrical Diaryl Ketones from Arenes
D. F. Taber, M. R. Sethuraman, J. Org. Chem., 2000, 65, 254-255.

Acylation and Related Reactions under Microwaves. 4. Sulfonylation Reactions of Aromatics
J. Marquié, A. Laporterie, J. Dubac, N. Roques, J.-R. Desmurs, J. Org. Chem., 2001, 66, 421-425.

Intramolecular Friedel-Crafts Acylation Reaction Promoted by 1,1,1,3,3,3-Hexafluoro-2-propanol
H. F. Motiwala, R. H. Vekariya, J. Aubé, Org. Lett., 2015, 17, 5484-5487.

Trifluoromethanesulfonic acid catalyzed Friedel-Crafts acylation of aromatics with β-lactams
K. W. Anderson, J. J. Tepe, Tetrahedron, 2002, 58, 8475-8481.

Reliable and Versatile Synthesis of 2-Aryl-Substituted Cinnamic Acid Esters
A. Ianni, S. R. Waldvogel, Synthesis, 2006, 2103-2112.

Titanium(IV) Chloride-Mediated Ortho-Acylation of Phenols and Naphthols
A. Bensari, N. T. Zaveri, Synthesis, 2003, 267-271.

Efficient Synthesis of β-Chlorovinylketones from Acetylene in Chloroaluminate Ionic Liquids
D. J. M. Snelders, P. J. Dyson, Org. Lett., 2011, 13, 4048-4051.

A General Method for the Synthesis of 3,5-Diarylcyclopentenones via Friedel-Crafts Acylation of Vinyl Chlorides
Y. Xu, M. McLaughlin, C.-y. Chen, R. A. Reamer, P. G. Dormer, I. W. Davies, J. Org. Chem., 2009, 74, 5100-5103.

Efficient, One-Pot, BF₃·OEt₂-Mediated Synthesis of Substituted N-Aryl Lactams
D. Caturvedi, A. K. Chaturvedi, N. Mishra, V. Mishra, Synlett, 2012, 23, 2627-2630.

A General Method for Acylation of Indoles at the 3-Position with Acyl Chlorides in the Presence of Dialkylaluminum Chloride
T. Okauchi, M. Itonaga, T. Minami, T. Owa, K. Kitoh, H. Yoshino, Org. Lett., 2000, 2, 1485-1487.

Synthesis of Indazolones via Friedel-Crafts Cyclization of Blocked (Masked) N-Isocyanates
E. B. Elkaeed, J. An, A. M. Beauchemin, J. Org. Chem., 2017, 82, 9890-9897.

Unified Approach to (Thio)chromenones via One-Pot Friedel-Crafts Acylation/Cyclization: Distinctive Mechanistic Pathways of β-Chlorovinyl Ketones
H. Y. Kim, E. Song, K. Oh, Org. Lett., 2017, 19, 312-315.