This account is focused on carbon-carbon, and carbon-sulphur bond-forming reactions through the use of carbon-and sulphur-centred radicals in water, respectively. It intends to show the scope and applications of these types of radicals with a synthetic goal, thus helping the radical synthetic chemist to grasp the fundamental aspects of the syntheses of a wide array of organic compounds through radical methods in environmentally friendly media. This account excludes the syntheses of organic substrates with the aid of organometallic/metal-centred radicals such as other Group IV-radicals and transition-metal radicals, and the important class of radical reductions currently accomplished in water using different metallic reducing species. The array of substrates synthesized through the present method encompasses intermolecular and intramolecular radical carbon-carbon bond formation reactions in water, and radical carbon-sulphur bond formation reactions. Among the radical carbon-carbon bond formation reactions, special attention is devoted to atom-transfer radical reactions, radical addition reactions to olefins, radical addition to carbon-nitrogen double bonds, the carboaminohydroxylation of alkenes, and the analogues of Knovonoegel reactions, the synthesis of functionalized enol ethers, thr carboazidation and azidation, and ynol formation, and radical cyclization reactions in water.
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