Sustainable cascade reaction combining transition metal-biocatalysis and hydrophobic substrates in surfactant-free aqueous solutions

•A cascade reaction consisting of a Heck reaction followed by an enzyme-catalyzed reaction is performed in surfactant-free aqueous solutions.•The cascade reaction is successfully performed in water in the absence of any solvent structuring.•The impact of the solvent on the solubility and stability of reaction components outweighs the need for solvent structuring.•A surfactant-free microemulsion can replace the micellar reaction solvent and allows the reaction temperature to be reduced.