Low melting mixtures based on β-cyclodextrin derivatives and N,N′-dimethylurea as solvents for sustainable catalytic processes

Abstract

Hydroformylation and Tsuji–Trost reactions were efficiently performed in low melting mixtures (LMMs) allowing the easy recyclability of the catalytic system.

Recent advances in the application of deep eutectic solvents as sustainable media as well as catalysts in organic reactions

“…140 In the case of the palladium-catalyzed cleavage of allyloctylcarbonate (Tsuji-Trost reaction), rapid conversion of allyloctylcarbonate was attained (5 min) at 90 °C in randomly methylated-β-CD (RAME-β-CD)/DMU under nitrogen with diethylamine as an allyl scavenger (Scheme 82). 140 In the case of the palladium-catalyzed cleavage of allyloctylcarbonate (Tsuji-Trost reaction), rapid conversion of allyloctylcarbonate was attained (5 min) at 90 °C in randomly methylated-β-CD (RAME-β-CD)/DMU under nitrogen with diethylamine as an allyl scavenger (Scheme 82).…”

Rhodium catalyzed hydroformylation of 1-decene in low melting mixtures based on various cyclodextrins and N,N′-dimethylurea

“…The first determinations of melting temperatures were realized at a ratio DMU/CD (70/30) since it was previously described that a melt was observed for DMU/α-CD [11] or DMU/β-CD [10] mixture at this ratio. For the three native CDs and the three hydroxypropylated CDs, the melting points were around 90°C and these latter were not significantly modified by the size of the cavity (i.e.…”

“…Different LMM mixtures based on carbohydrate/ urea (or its derivatives) have been used as reaction medium for organometallic catalytic processes in the cases of palladium-catalyzed Suzuki coupling [6], rhodium-catalyzed hydrogenation reaction [6], palladiumcatalyzed Stille cross-coupling [7], palladium-catalyzed Heck and Sonogashira coupling [8] while ruthenium-catalyzed isomerization reaction was performed in choline chloride/glycerol mixture [9]. Very recently, our group has published new LMMs based on β-cyclodextrin (β-CD) series and N,N′-dimethylurea (DMU) to perform palladiumcatalyzed Tsuji-Trost and rhodium-catalyzed hydroformylation reactions [10]. These LMMs were simply prepared by mixing DMU and different β-CDs at a weight ratio of 70/30.…”

Deep Eutectic Solvents: Environmentally Friendly Media for Metal-Catalyzed Organic Reactions

“…Apart from C-C coupling reactions, other palladium catalyzed organic reactions have been successfully performed in different DESs. In this sense, Jérôme, Tilloy and co-workers reported in 2014 the palladium-catalyzed cleavage of allylcarbonates (Tsuji-Trost reaction) using new low melting mixtures based on β-cyclodextrines and DMU (80). The cleavage of the desired allylcarbonate was carried out at 90 ºC under nitrogen with diethylamine as an allyl scavenger.…”