High yield room temperature synthesis of pyranochromenes in neutral cetyltrimethylammonium bromide micellar media

Pyrano[3,2-c]chromene derivatives are heterocycles with a wide range of biological properties. There is actually a need for safer synthesis of heterocycles, using for instance water as a solvent. High selectivity can also be achieved by addition of surface-active reagents to form micelles. Indeed, it is presumed that water facilitates organic reactions by the hydrophobic effect, enhanced hydrogen bonding in the transition state and cohesive energy density. Here, a simple aqueous-mediated protocol is developed for the quantitative synthesis of medicinally relevant pyrano[3,2-c]chromene derivatives by the tandem reaction of readily available reagents in cetyltrimethylammonium bromide micellar media. This new method is a modification of the three-component reaction involving Knoevenagel condensation, Michael addition and cyclization reaction. Yields of 3, 4-dihydropyrano[c]chromenes ranged from 85 to 99 % at room temperature.     

Efficient synthesis of α,β-unsaturated ketones with trans-selective Horner–Wadsworth–Emmons reaction in water

Organic reactions in aqueous media are being developed because water is environmentally benign. The Horner–Wadsworth–Emmons reaction is a modified Wittig reaction for the synthesis of α,β-unsaturated ketones and other conjugated compounds. Here we prepared high molecular weight ketones by the Horner–Wadsworth–Emmons reaction of dimethyl-2-oxopropylphosphonate and various aldehydes in water at room temperature. The product was precipitated during the reaction process and was separated readily by a simple filtration in 90–99 % yield.     

Fast 62–92 % yield preparation of amino acid dithiocarbamates in green solvent at room temperature

Dithiocarbamate and their derivatives are of importance in medicinal chemistry due to their biological activities, in agriculture as fungicides and in organic synthesis as versatile synthetic intermediates. Green solvents such as deep eutectic solvents and polyethylene glycol are new emerging alternatives to conventional harmful organic solvents. Here, we report the synthesis of amino acid–based dithiocarbamates by one-pot three-component reaction of the electrophilic reagent, carbon disulfide and α-amino acids in deep eutectic solvent and polyethylene glycol as a catalyst and reaction media. In situ preparation of dithiocarbamates by the reaction of different amino acids and carbon disulfide, followed by addition reaction with epoxides, alkyl halides and α, β-unsaturated enones at room temperature, gave the corresponding products in 62–92 % yield with a short reaction time without any tedious workup procedures. The deep eutectic solvents and polyethylene glycol were recycled without activity or yield decrease. Therefore, the synthesis of amino acid–based dithiocarbamates in green solvents is a promising alternative to previously used procedures.