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This method is characterized by a single\u2010pot, low\u2010temperature hydrocarboxylation reaction of the cycloalkane with carbon monoxide, water and potassium peroxodisulfate in water\/acetonitrile medium, proceeding either in the absence or in the presence of a metal promoter. The influence of various reaction parameters, such as type and amount of metal promoter, solvent composition, temperature, time, carbon monoxide pressure, oxidant and cycloalkane, is investigated, leading to an optimization of the cyclohexane and cyclopentane carboxylations. The highest efficiency is observed in the systems promoted by a tetracopper(II) triethanolaminate\u2010derived complex, which also shows different bond and stereoselectivity parameters (compared to the metal\u2010free systems) in the carboxylations of methylcyclohexane and stereoisomeric 1,2\u2010dimethylcyclohexanes. A free radical mechanism is proposed for the carboxylation of cyclohexane as a model substrate, involving the formation of an acyl radical, its oxidation and consequent hydroxylation by water. Relevant features of the present hydrocarboxylation method, besides the operation in aqueous medium, include the exceptional metal\u2010free and acid\u2010solvent\u2010free reaction conditions, a rare hydroxylating role of water, substrate versatility, low temperatures (<jats:italic>ca.<\/jats:italic> 50\u2009\u00b0C) and a rather high efficiency (up to 72% carboxylic acid yields based on cycloalkane).<\/jats:p>","DOI":"10.1002\/adsc.200900537","type":"journal-article","created":{"date-parts":[[2009,11,18]],"date-time":"2009-11-18T14:34:46Z","timestamp":1258554886000},"page":"2936-2948","source":"Crossref","is-referenced-by-count":61,"title":["Metal\u2010Free and Copper\u2010Promoted Single\u2010Pot Hydrocarboxylation of Cycloalkanes to Carboxylic Acids in Aqueous Medium"],"prefix":"10.1002","volume":"351","author":[{"given":"Marina\u2005V.","family":"Kirillova","sequence":"first","affiliation":[]},{"given":"Alexander\u2005M.","family":"Kirillov","sequence":"additional","affiliation":[]},{"given":"Armando J.\u2005L.","family":"Pombeiro","sequence":"additional","affiliation":[]}],"member":"311","published-online":{"date-parts":[[2009,11,24]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","doi-asserted-by":"crossref","DOI":"10.1007\/0-306-46945-6","volume-title":"Activation and Catalytic Reactions of Saturated Hydrocarbons in the Presence of Metal Complexes","author":"Shilov A. 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