{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,7,22]],"date-time":"2026-07-22T21:14:45Z","timestamp":1784754885482,"version":"3.55.0"},"reference-count":98,"publisher":"MDPI AG","issue":"18","license":[{"start":{"date-parts":[[2022,9,14]],"date-time":"2022-09-14T00:00:00Z","timestamp":1663113600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>In this review, we discuss Friedel-Crafts-type aromatic amidation and acylation reactions, not exhaustively, but mainly based on our research results. The electrophilic species involved are isocyanate cation and acylium cation, respectively, and both have a common +C=O structure, which can be generated from carboxylic acid functionalities in a strong Br\u00f8nsted acid. Carbamates substituted with methyl salicylate can be easily ionized to the isocyanate cation upon (di)protonation of the salicylate. Carboxylic acids can be used directly as a source of acylium cations. However, aminocarboxylic acids are inert in acidic media because two positively charged sites, ammonium and acylium cation, will be generated, resulting in energetically unfavorable charge-charge repulsion. Nevertheless, the aromatic acylation of aminocarboxylic acids can be achieved by using tailored phosphoric acid esters as Lewis bases to abrogate the charge-charge repulsion. Both examples tame the superelectrophilic character.<\/jats:p>","DOI":"10.3390\/molecules27185984","type":"journal-article","created":{"date-parts":[[2022,9,14]],"date-time":"2022-09-14T23:16:36Z","timestamp":1663197396000},"page":"5984","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":20,"title":["Friedel-Crafts-Type Acylation and Amidation Reactions in Strong Br\u00f8nsted Acid: Taming Superelectrophiles"],"prefix":"10.3390","volume":"27","author":[{"given":"Akinari","family":"Sumita","sequence":"first","affiliation":[{"name":"Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5390-0203","authenticated-orcid":false,"given":"Tomohiko","family":"Ohwada","sequence":"additional","affiliation":[{"name":"Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2022,9,14]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"40061","DOI":"10.1039\/C8RA07325B","article-title":"Applications of Friedel\u2013Crafts reactions in total synthesis of natural products","volume":"8","author":"Heravi","year":"2018","journal-title":"RSC Adv."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"2635","DOI":"10.1002\/ejoc.200901492","article-title":"Organocatalyzed Asymmetric Friedel\u2013Crafts Reactions","volume":"14","author":"Terrasson","year":"2010","journal-title":"Eur. 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