作者：Ming Luo, Xing-Hong Zhang,* and Donald J. Darensbourg*
关键字：Poly(monothiocarbonate), Carbonyl Sulfide, Epoxides
论文来源：期刊
具体来源：Accounts of Chemical Research 2016, 49, 2209-2219.
发表时间：2016年

CONSPECTUS: Carbonyl sulfide (COS) is an air pollutant that causes acid rain, ozonosphere damage, and carbon dioxide (CO₂) generation. It is a heterocumulene and structural analogue of CO₂. Relevant to organic synthesis, it is a source of C=O or C=S groups and thus an ideal one-carbon (C1) building block for synthesizing sulfur-containing polymers through the similar route of CO₂ copolymerization. In contrast, traditional synthesis of sulfur-containing polymers often involves the condensation of thiols with phosgene and ring-opening polymerization of cyclic thiocarbonates that are generally derived from thiols and phosgene; thus, COS/epoxide copolymerization is a “greener” route to supplement or supplant current processes for the production of sulfur-containing polymers. This Accounts highlights our efforts on the discovery of the selective formation of poly(monothiocarbonate)s from COS with epoxides via heterogeneous zinc-cobalt double metal cyanide complex (Zn?Co(III) DMCC) and homogeneous (salen)CrX complexes. The catalytic activity and selectivity of Zn?Co(III) DMCC for COS/epoxide copolymerization are similar to those for CO₂/epoxide copolymerization. (salen)CrX complexes accompanied by onium salts exhibited high activity and selectivity for COS/epoxide copolymerization under mild conditions, affording copolymers with >99% monothiocarbonate units and high tail to-head content up to 99%. By way of contrast, these catalysts often show moderate or low activity for CO₂/epoxide copolymerization. Of note, a specialty of COS/epoxide copolymerization is the occurrence of an oxygen?sulfur exchange reaction (O/S ER), which may produce carbonate and dithiocarbonate units. O/S ER, which are induced by the metal?OH bond regenerated by chain transfer reactions, can be kinetically inhibited by changing the reaction conditions. We provide a thorough mechanistic understanding of the electronic/steric effect of the catalysts on the regioselectivity of COS copolymerization. The regioselectivity of the copolymerization originates from the solely nucleophilic attack of the sulfur anion to methylene of the epoxide, and thus, the chiral configuration of the monosubstituted epoxides is retained. COS-based copolymers are highly transparent sulfur-containing polymers with excellent optical properties, such as high refractive index and Abbe number. Thanks to their good solubility and many available epoxides, COS/epoxide copolymers can potentially be a new applicable optical material. Very recently, crystalline COS-based polymers with or without chiral carbons have been synthesized, which may further expand the scope of application of these new materials.