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The approach is based on a metal\u2010free or copper\u2010promoted reaction of ethane, propane or <jats:italic>n<\/jats:italic>\u2010butane with carbon monoxide and water, in a H<jats:sub>2<\/jats:sub>O\/MeCN medium at 50\u201360\u2009\u00b0C, in the presence of potassium peroxodisulfate. The effects of various reaction parameters, such as the absence or presence of a copper promoter, solvent composition, temperature, time, CO and alkane pressure, were studied. A free radical mechanism was confirmed by radical trap experiments involving acyl radical formation, oxidation and subsequent hydroxylation by water. Remarkable yields (based on alkane) of carboxylic acids in the 34\u201341\u2009% range were achieved even in the metal\u2010free systems, although in the presence of a tetracopper(II) triethanolaminate derived promoter they reach superior values of 58 and 87\u2009% for the hydrocarboxylations of propane and <jats:italic>n<\/jats:italic>\u2010butane, respectively; in these cases, branched isobutyric and 2\u2010methylbutyric acids were the predominant products. From a green perspective, important features of the present alkane hydrocarboxylations include the exceptional metal\u2010free, mild and acid\u2010solvent\u2010free reaction conditions, the operation in aqueous medium with a rare hydroxylating role of water, with high selectivities, and yields of carboxylic acids. Taken together, these conditions correspond to the mildest and the most efficient method so far reported for the oxidative functionalisation of gaseous alkanes.<\/jats:p>","DOI":"10.1002\/chem.201000352","type":"journal-article","created":{"date-parts":[[2010,5,7]],"date-time":"2010-05-07T20:38:33Z","timestamp":1273264713000},"page":"9485-9493","source":"Crossref","is-referenced-by-count":61,"title":["Mild, Single\u2010Pot Hydrocarboxylation of Gaseous Alkanes to Carboxylic Acids in Metal\u2010Free and Copper\u2010Promoted Aqueous Systems"],"prefix":"10.1002","volume":"16","author":[{"given":"Marina\u2005V.","family":"Kirillova","sequence":"first","affiliation":[]},{"given":"Alexander\u2005M.","family":"Kirillov","sequence":"additional","affiliation":[]},{"given":"Armando\u2005J.\u2005L.","family":"Pombeiro","sequence":"additional","affiliation":[]}],"member":"311","published-online":{"date-parts":[[2010,8,12]]},"reference":[{"unstructured":"\u00a0","key":"e_1_2_6_1_2"},{"volume-title":"Sustainable Strategies for the Upgrading of Natural Gas: Fundamentals, Challenges, and Opportunities","year":"2005","key":"e_1_2_6_2_2"},{"doi-asserted-by":"publisher","key":"e_1_2_6_3_2","DOI":"10.1002\/9783527619405.ch5b"},{"key":"e_1_2_6_4_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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