Abstract

This review is dedicated to the state-of-the art routes used for the synthesis of CO2-based (a)cyclic carbonates and polycarbonates from alcohol substrates, with an emphasis on their respective main advantages and limitations. The first section reviews the synthesis of organic carbonates such as dialkyl carbonates or cyclic carbonates from the carbonation of alcohols. Many different synthetic strategies have been reported (dehydrative condensation, the alkylation route, the “leaving group” strategy, the carbodiimide route, the protected alcohols route, etc.) with various substrates (mono-alcohols, diols, allyl alcohols, halohydrins, propargylic alcohols, etc.). The second section reviews the formation of polycarbonates via the direct copolymerization of CO2 with diols, as well as the ring-opening polymerization route. Finally, polycondensation processes involving CO2-based dimethyl and diphenyl carbonates with aliphatic and aromatic diols are described.

Highlights

  • Today, our modern society is facing climate change and ocean acidification caused by the continuous increase in CO2 levels within the atmosphere

  • This review provides an overview of the progress made in the synthesis of (a)cyclic and polymeric carbonates from alcohols substrates

  • The ketal decomposes in situ into the former ketone and an alcohol that is subsequently involved in a cascade coupling reaction with CO2 to afford the acyclic carbonate (Scheme 9)

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Summary

Introduction

Our modern society is facing climate change and ocean acidification caused by the continuous increase in CO2 levels within the atmosphere. The growth of which is inter-seasonal and requires multi-step post-treatment (extraction, fractionation, fermentation, etc.) prior to valorization, CO2 is a cheap and renewable carbon source that is regenerated instantaneously and locally This resource may undergo numerous chemical processes and syntheses to design existing organic molecules or polymers or new (sophisticated) ones [4,5,6]. Despite being very attractive and produced via facile oxidation of olefins, including natural ones derived from vegetable oils or terpenes, epoxides display acute toxicity, as they act as alkylating agents capable of binding with DNA [14,15] In this context, the replacement of epoxides with safe and easy-to-handle (renewable) substrates to synthesize organic carbonates and polycarbonates is gaining huge interest in the scientific community.

R OH OH OH
Synthesis of Acyclic Organic Carbonates
DMC Synthesis by Dehydrative Condensation
Synthesis of Acyclic Carbonates via the Alkylation Route
Synthesis of Acyclic Carbonates via the Carbodiimide Route
Synthesis of Acyclic Carbonates from the “Protected Alcohols” Route
Synthesis of Cyclic Organic Carbonates
Synthesis of Cyclic Carbonates from Diols
Direct Copolymerization by Dehydrative Polycondensation
Direct Copolymerization via Alkylation
Terpolymerriizzaattiioonn MMeetthhooddss
Ring-Opening Polymerization of Cyclic Carbonates
DMC and DPC as Carbonylating Agents
Findings
Conclusions
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