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Direct amidation of aromatic compounds by isocyanate cations generated at room temperature from carbamoyl salicylates in trifluoromethanesulfonic acid (TfOH) was examined. Carbamates with <jats:italic>ortho<\/jats:italic>\u2010salicylate as an ether group (carbamoyl salicylates) showed dramatically accelerated O\uf8ffC bond dissociation in TfOH, which resulted in facile generation of the isocyanate cation. These chemoselective intermolecular aromatic amidation reactions proceeded even at room temperature and showed good compatibility with other electrophilic functionalities and high discrimination between <jats:italic>N<\/jats:italic>\u2010monosubstituted carbamate and <jats:italic>N<\/jats:italic>,<jats:italic>N<\/jats:italic>\u2010disubstituted carbamate. The reaction rates of secondary and tertiary amide formation were markedly different, and this difference was utilized to achieve successive (tandem) amidation reactions of molecules with an <jats:italic>N<\/jats:italic>\u2010monosubstituted carbamate and an <jats:italic>N<\/jats:italic>,<jats:italic>N<\/jats:italic>\u2010disubstituted carbamate with two kinds of aromatic compounds.<\/jats:p>","DOI":"10.1002\/asia.201402625","type":"journal-article","created":{"date-parts":[[2014,8,19]],"date-time":"2014-08-19T16:41:12Z","timestamp":1408466472000},"page":"2995-3004","source":"Crossref","is-referenced-by-count":16,"title":["Acid\u2010Promoted Chemoselective Introduction of Amide Functionality onto Aromatic Compounds Mediated by an Isocyanate Cation Generated from Carbamate"],"prefix":"10.1002","volume":"9","author":[{"given":"Akinari","family":"Sumita","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Hiroaki","family":"Kurouchi","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Yuko","family":"Otani","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Tomohiko","family":"Ohwada","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2014,8,19]]},"reference":[{"key":"e_1_2_6_1_2","volume-title":"The Amide Linkage: Structural Significance in Chemistry, Biochemistry, and Materials Science","year":"2000"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1038\/nature10702"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo9606564"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol203007s"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200503991"},{"key":"e_1_2_6_5_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200503991"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.1145295"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1039\/B701677H"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja906005j"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.287.5460.2007"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol006054v"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol0060174"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0294919"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(98)00017-3"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(98)00018-5"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol701583t"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1002\/macp.1973.021670102"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol901370y"},{"key":"e_1_2_6_18_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol200531k"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja800612r"},{"key":"e_1_2_6_20_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201204481"},{"key":"e_1_2_6_20_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201204481"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1002\/cber.19640970222"},{"key":"e_1_2_6_22_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00804a022"},{"key":"e_1_2_6_23_2","doi-asserted-by":"publisher","DOI":"10.1039\/c2cc34062c"},{"key":"e_1_2_6_24_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo3020566"},{"key":"e_1_2_6_25_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.tetlet.2012.06.135"},{"key":"e_1_2_6_26_2","doi-asserted-by":"publisher","DOI":"10.1039\/j29680001099"},{"key":"e_1_2_6_27_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201402447"},{"key":"e_1_2_6_28_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja067682w"},{"key":"e_1_2_6_29_2","doi-asserted-by":"publisher","DOI":"10.1039\/j29690000934"},{"key":"e_1_2_6_30_2","doi-asserted-by":"publisher","DOI":"10.1021\/ef00001a005"},{"key":"e_1_2_6_31_2","unstructured":"\u00a0"},{"key":"e_1_2_6_32_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo800674h"},{"key":"e_1_2_6_33_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja908749u"},{"key":"e_1_2_6_34_2","unstructured":"The present kinetic study has practical limitations; kinetic experiments can be carried out only under conditions in which a mixture of aromatic compound (such asp\u2010xylene4\u2009b) and TfOH gives a homogenous solution. 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