Halo alcohol dehalogenase HheC catalyzes the highly enantioselective dehalogenation of vicinal halo alcohols to epoxides, as well as the reverse reaction, the enantioselective and beta-regioselective nucleophilic ring opening of epoxides by pseudo-halides such as azide and cyanide. To investigate this latter reaction, we determined X-ray structures of complexes of HheC with the favored and unfa...

A hyperresponsive tool to assess supramolecular catalysis, the cyclization of di-epoxides into cyclic ethers is used elucidate difference between pnictogen-bonding and Lewis acid catalysis systematically. For all stereoisomers, most tested catalysts follow Baldwin rules. Brønsted anion–? afford almost only products. acids such as SbCl3, BF3 BiCl3 give poorest selectivity, with at least 50 % (B)...

Aromatic hydroxylation reactions catalyzed by heme-thiolate enzymes proceed via an epoxide intermediate. These aromatic epoxides could be valuable building blocks for organic synthesis giving access to a range of chiral trans-disubstituted cyclohexadiene synthons. Here, we show that naphthalene generated fungal peroxygenases can subjected nucleophilic ring opening, yielding non-racemic derivate...

Controlled routes to prepare polyesters and polycarbonates are of interest due to the widespread application of these materials and the opportunities provided to prepare new copolymers. Furthermore, ring-opening copolymerization may enable new poly(ester-carbonate) materials to be prepared which are inaccessible using alternative polymerizations. This review highlights recent advances in the ri...

The alternating copolymerization of epoxides and cyclic anhydrides is an increasingly popular route to aliphatic polyesters that are of interest as biodegradable replacements for petroleum-based polymers and for use in the biomedical field. However, broad and bimodal molecular weight distributions in these polymerizations continues to be an issue, limiting synthesis of multiblock copolymers. By...

•Unprecedented zirconocene catalysis in reductive ring opening of epoxides•Broad reactivity across diverse substrates, including natural products•Reverse regioselectivity compared with the well-established methods titanocene•Changing metal center metallocene alters reversibility Epoxides are key structural motifs commonly found products and medicinal agrochemical agents as well various intermed...