Aqueous micellar media have emerged as sustainable alternatives to organic solvents for small-molecule synthesis. This Review discusses the evolution of surfactants for synthesis, their application to cross-coupling reactions, the benefits for reactivity and sustainability, and the remaining challenges in this rapidly growing field.

Thanks to their ability to efficiently and reliably construct carbon–carbon and carbon–heteroatom bonds, cross-coupling reactions remain at the forefront of chemical research in both academic and industrial settings. However, the growing emphasis on sustainability has exposed the shortcomings of cross-coupling chemistry in several areas, including the preponderance toward toxic polar aprotic solvents, high loadings of precious metal catalysts, and production of large quantities of waste. In recent years, micellar reaction media, formed by dissolution of surfactant molecules in water, have emerged as a sustainable alternative to organic solvents, allowing for use of water as the bulk medium while circumventing the usual solubility issues associated with its use. This Review introduces the fundamentals of surfactants for synthesis and summarizes recent advances in cross-coupling chemistry in micellar media, with a focus on improving both sustainability and reaction performance using micellar technologies.