Organic carboxylate salt-enabled alternative synthetic routes for bio-functional cyclic carbonates and aliphatic polycarbonates

Abstract

A cyclic carbonate with an ammonium carboxylate residue was found to serve as a nucleophile for esterification with alkyl bromides via the SN2 mechanism.

Organocatalyzed ring-opening reactions of γ-carbonyl-substituted ε-caprolactones

“…We have found that functional poly(trimethylene carbonate) (PTMC) analogues with methoxyalkyl ester side chains exhibit excellent antiplatelet properties. 19,20 These results further lead to the recent developments of ether-functionalized PTMC and polydioxanone. 21–23 However, biodegradation of the PTMC analogues proceeds slowly compared to that of aliphatic polyesters.…”

Sustainable and Recyclable Polymers from CO2 and Lignin: Enabling Waste to Wealth Transformation

“…Investigations have been conducted on the use of CO 2 as a raw material in the synthesis of ureas, 28 organic carbonates, 29 carbamates, 30 and polycarbonates. [31][32][33] To synthesize aliphatic polycarbonates from CO 2 , four well-developed synthetic routes have been developed, including polycondensation of aliphatic diols with phosgene derivatives or dialkyl carbonates, 31 copolymerizations of CO 2 with epoxides, [34][35][36] direct polymerization of CO 2 , 33,[37][38][39] and ring-opening polymerization of cyclic carbonate monomers. 31,32,40 Conventionally, hazardous phosgene has been used as a raw material in industrial processes to prepare polycarbonates, which produce a lot of salt waste.…”

“…[31][32][33] To synthesize aliphatic polycarbonates from CO 2 , four well-developed synthetic routes have been developed, including polycondensation of aliphatic diols with phosgene derivatives or dialkyl carbonates, 31 copolymerizations of CO 2 with epoxides, [34][35][36] direct polymerization of CO 2 , 33,[37][38][39] and ring-opening polymerization of cyclic carbonate monomers. 31,32,40 Conventionally, hazardous phosgene has been used as a raw material in industrial processes to prepare polycarbonates, which produce a lot of salt waste. 37 Although copolymerization of epoxides or oxetanes with CO 2 has been investigated, direct polymerization from CO 2 as a carbonyl source will be ideal.…”

Ring-opening polymerization of functionalized aliphatic bicyclic carbonates

“…7,8 Larger ring cyclic carbonates such as 6MCCs over time have become popular monomers but are often prepared using harmful and low-atom economy reagents such as phosgene and its derivatives (Scheme 1a). 9…”

“…7,8 Larger ring cyclic carbonates such as 6MCCs over time have become popular monomers but are often prepared using harmful and low-atom economy reagents such as phosgene and its derivatives (Scheme 1a). 9 Our group recently reported a simple catalytic CO 2 -based approach towards bicyclic 6MCCs (Scheme 1b). 10,11 This approach benefits from a double and cooperative activation strategy with a pendent alcohol group activating CO 2 while an Al-complex promotes intramolecular ring-opening of the oxirane in the substrate through coordination.…”