Catalytic allylic arylation of cinnamyl carbonates over palladium nanoparticles supported on a thermoresponsive polymer in water

Abstract

Poly(NIPAM-co-4-VP) undergoes a phase transition at the low critical solution temperature with a change from the hydrophilic to the hydrophobic core in a hydrophilic solvent. Palladium nanoparticles supported on such a thermoresponsive polymer support were demonstrated to catalyze the Tsuji-Trost reaction for the arylation of various cinnamyl carbonates by arylboronic acids. Therefore, a protocol developed using mild reaction conditions demonstrates the recyclability of the catalyst in an eco-friendly solvent such as water. Fig. 1 Preparation of the Pd(0) catalyst supported on poly(NIPAM-co-4-VP). † Electronic supplementary information (ESI) available. See Results and discussionPolymer behaviour and morphology According to differential scanning calorimetry (DSC) studies, the polymer coils around itself and results in behavioural changes from the hydrophilic to hydrophobic polymer core in a hydrophilic solvent like water. Fig. 2 Transmission Electron Microscopy (TEM) images of the Pd(0) catalyst supported on poly(NIPAM-co-4-VP).

Ultrasound irradiation as an effective tool in synthesis of the slag-based catalysts for carboxymethylation

“…The current process produces cinnamyl methyl carbonate (product I) as the main and desired compound with some amounts of the side products. The desired product I finds its application in organic synthesis [11] and can be used in the synthesis of biologically active compounds [12] , [13] , [14] . Numerous solid basic catalysts (K 2 CO 3 , CsF/αAl 2 O 3 , NaOH, MgO, hydrotalcite, NaAlO 2 ) were utilized as catalysts for carboxymethylation of various alcohols with dimethyl carbonate under different temperatures (90–180 °C) and reaction time (up to 96 h) [15] , [16] , [17] .…”

Carboxymethylation of Cinnamyl Alcohol with Dimethyl Carbonate over Graphitic Carbon Nitrides

“…Carbonate esters not only serve as important building blocks in organic synthesis [1] capable to undergo, for instance, asymmetric allylic alkylation [2] and substitution, [3] allylic arylation, [4] the Tsuji‐Trost allylation, [5] but also as protecting agents of alcohols and phenols owing to their high stability, especially in basic media [6,7] . In addition, carbonate esters arouse interest as green solvents, fuel additives as well as lubricating oils [8,9] …”

Carboxymethylation of cinnamylalcohol with dimethyl carbonate over the slag-based catalysts

“…1) as a green reactant and solvent produces cinnamyl methyl carbonate (product I), a valuable carbonate ester, as the main and the desired compound with some amounts of the side products [4]. Carbonate ester finds its application as an allylic electrophile affording the alkylated products in organic synthesis, namely the Tsuji-Trost reaction and asymmetric allylic substitution [5][6][7]. At the same time cinnamyl methyl carbonate can be utilized for phenol group protection [8] and used in synthesis of biologically active compounds [7,9,10].…”

“…Carbonate ester finds its application as an allylic electrophile affording the alkylated products in organic synthesis, namely the Tsuji-Trost reaction and asymmetric allylic substitution [5][6][7]. At the same time cinnamyl methyl carbonate can be utilized for phenol group protection [8] and used in synthesis of biologically active compounds [7,9,10].…”