A simple preparation on gram-scale of thiocyanate derivatives via nucleophilic substitution of halogenated compounds with SCN salts at high substrate concentrations in a few minutes and excellent yields was successfully accomplished in hydroalcoholic media. The obtained compounds were employed for the efficient synthesis of valuable 5-aryl-2-imino-1,3-oxathiolane derivatives (a one-pot approach is also presented).

Multi‐step processes catalysed by several catalysts working concurrently have been developed in nature, thus improving reaction efficiency. The quest for novel and improved catalytic systems has led to the development of biocatalytic and later to organocatalytic procedures as very valuable tools in asymmetric synthesis while using mild reaction conditions in the absence of metal catalysts. As a timeless challenge, chemists are facing the need for process designs in which different sorts of catalysts can operate successfully in a one‐pot concurrent fashion. Likewise, such designs bring about the best of each catalyst and, in certain cases, enable us to improve problematic issues, such as reactivity, selectivity, solubility, inhibition, etc. Specifically, to combine these two types of catalysts in one‐pot, achieving high yields and selectivity, is a fascinating aspect of catalysis. This review covers representative advances in this field, in particular those in which biocatalysts and organocatalysts are employed either in sequential reactions or in simultaneous processes. magnified image

A fully convergent one-pot two-step synthesis of different chiral 1,2,3-triazole-derived diols in high yields and excellent enantio- and diastereoselectivities has been achieved under very mild conditions in aqueous medium by combining a single alcohol dehydrogenase (ADH) with a Cu-catalysed ‘click’ reaction.