A Switchable Domino Process for the Construction of Novel CO2‐Sourced Sulfur‐Containing Building Blocks and Polymers. (18th July 2019)

• Record Type: Journal Article
• Authors: Ouhib, Farid; Grignard, Bruno; Van Den Broeck, Elias; Luxen, André; Robeyns, Koen; Van Speybroeck, Veronique; Jerome, Christine; Detrembleur, Christophe
• Is Part Of: Angewandte Chemie. Volume 131:Number 34(2019)
• Page Start: 11894
• Page End: 11899
• Publication Date: 2019-07-18
• Subjects: Dominoprozesse -- Kohlendioxid -- Organokatalyse -- Polymerisation -- Synthesemethoden; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201905969
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: α‐Alkylidene cyclic carbonates (αCCs) recently emerged as attractive CO2 ‐sourced synthons for the construction of complex organic molecules. Herein, we report the transformation of αCCs into novel families of sulfur‐containing compounds by organocatalyzed chemoselective addition of thiols, following a domino process that is switched on/off depending on the desired product. The process is extremely fast and versatile in substrate scope, provides selectively linear thiocarbonates or elusive tetrasubstituted ethylene carbonates with high yields following a 100 % atom economy reaction, and valorizes CO2 as a renewable feedstock. It is also exploited to produce a large diversity of unprecedented functional polymers. It constitutes a robust platform for the design of new sulfur‐containing organic synthons and important families of polymers. Abstract : Hohe Atomökonomie : Lineare Thiocarbonate und schwer zu fassende, tetrasubstituierte Ethylencarbonate sind in hohen Ausbeuten durch organokatalytische chemoselektive Addition von Thiolen an cyclische α‐Alkylidencarbonate über einen schaltbaren Dominoprozess zugänglich. Die robuste Methode wurde auch zum leichten Aufbau einer Vielfalt neuartiger S‐haltiger Polymere genutzt.