Poly(thioether)s from Closed-System One-Pot Reaction of Carbonyl Sulfide and Epoxides by Organic Bases

Abstract

The synthesis of poly­(thioether), a highly desired sulfur-containing polymer, is still a key challenge. Herein, we report a simple and facile approach to poly­(thioether)­s by closed-system one-pot reaction of carbonyl sulfide (COS) and epoxides. This route underwent the coupling reaction of COS with epoxides, followed by decarboxylative ring-opening polymerization (ROP) of the generated mixed cyclic thiocarbonates with releasing of CO2 and a little bit of COS. Organic base was used as catalyst and initiator in the two steps, respectively. The oxygen/sulfur exchange reaction was driven by successive regioselective elementary reactions and spontaneous releasing of CO2 (COS), leading to the sulfur atom of COS transferring to poly­(thioether)­s, which was well demonstrated by DFT studies. This work provides an easy-to-handle, metal-free route to poly­(thioether)­s bearing diverse structures by using readily available chemicals.

Polymers from sugars and CS2: ring opening copolymerisation of a d-xylose anhydrosugar oxetane

“…under UV radiation). 19,21 The synthesis of polythiocarbonates is possible through polycondensation, [22][23][24][25] the ring-opening polymerisation (ROP) of cyclic thiocarbonates, 26,27 polyalkylation of trithiocarbonates 28,29 or the ring-opening copolymerisation (ROCOP) of CS 2 15, 30-33 and COS 11,[34][35][36][37][38] with cyclic ethers (epoxides and oxetane). ROCOP methods are particularly interesting given the array of synthetic possibilities provided by the pool of cyclic ethers usable, coupled with the polymerisation control brought by existing ROCOP catalysts.…”

Highly Z‐Selective Synthesis of Highly Substituted 1,3‐Oxathiolane‐2‐imines via TfOH‐Catalyzed Formal [3+2] Cycloaddition of Donor‐Acceptor Oxiranes and Isothiocyanates

“…The cycloaddition of 1 a (1.0008 g) and 2 a proceeded smoothly under the standard reaction condition to afford the desired product 3 a in 89 % yield (Scheme 2a). Furthermore, 3 a were efficiently transformed into 1,3-oxathiolane-2-one 4, which is a valuably synthetic intermediate in organic synthesis [25] and polymer sciences [26] (Scheme 2b).…”

Facile Synthesis of Well‐Defined Branched Sulfur‐Containing Copolymers: One‐Pot Copolymerization of Carbonyl Sulfide and Epoxide

“…The precise synthesis of sulfur‐containing polymers has made great progress in view of their outstanding characteristics such as good optical properties, remarkable chemical resistance, and excellent heavy metal capture abilities . Poly(monothiocarbonate) is a promising class of sulfur‐containing polymers because of its potential biodegradability as it contains ester linkages in the backbones.…”

“…The precise synthesis of sulfur-containing polymers has made great progress in view of their outstanding characteristics such as good optical properties, remarkable chemical resistance, and excellent heavy metal capture abilities. [9][10][11][12][13][14][15] Poly(monothiocarbonate) is a promising class of sulfurcontaining polymers because of its potential biodegradability as it contains ester linkages in the backbones. The main synthetic approaches to poly(monothiocarbonate) include the polycondensation of dithiols and phosgene (or thiophosgene) [16] or the ring-opening polymerization of cyclic thiocarbonates.…”