278-84-2

This work demonstrates a novel strategy that the introduction of non-redox metal ions as Lewis acids to the classic dinuclear manganese complex [MnIV2(μ-O)3(Me3tacn)2](PF6)2 can greatly promote the alkene epoxidation efficiency under mild conditions with H2O2 as the solely terminal oxidant because of its economic and environmental advantages. When [MnIV2(μ-O)3(Me3tacn)2](PF6)2 was used as the catalyst in the absence of Lewis acids, only 16.4% conversion of cyclooctene with 6.2% yield of epoxide was obtained and the obvious decomposition of H2O2 was observed. However, the oxygen transfer efficiency of the catalyst was sharply improved with 100% conversion and 90.2% yield of epoxide under identical conditions when the non-redox metal ion, such as Sc3+, was introduced to the catalytic system. The novel strategy was successfully applied to the epoxidation reactions of different types of alkenes. Through UV–vis, FT-IR, EPR and CV characterizations, it was evidenced that the non-redox metal ions with high positive charge as Lewis acids could dissociate the sluggish dinuclear Mn-(μ-O)3-Mn core and the open-loop dinuclear manganese complex, HO-MnIII-(μ-O)-MnIV = O or O = MnIV-(μ-O)-MnIV = O, was proposed as the active species, which was capable of the alkene epoxidation process. This work illustrated an alternative protocol to manipulate the reactivity of those sluggish catalysts by the introduction of non-redox metal ions and provided clues to understand the role of non-redox metal ions in metalloenzymes and heterogeneous catalysts.

Enzyme (pig liver esterase and lipase from Aspergillus niger)-catalysed enantioselective hydrolyses of racemic diacetates, (1R*,2S*,4R*,5S*)-, and (1R*,2R*,4R*,5R*)-2,5-diacetoxybicycloheptanes, (1R*,2S*,4R*,5S*)-, (1R*,2R*,4R*,5R*)- and (1R*,2R*,4R*,5S*)-2,5-diacetoxybicyclooctanes, (2R*,3R*)-2,3-diacetoxybicyclooctane and (1R*,2S*,6S*,8R*)- and (1R*,2S*,6S*,8S*)-2,8-diacetoxybicyclooctanes gave the corresponding monoacetates and the recovered diacetates in an optically active form.The absolute configurations of the products wereunequivocally determined by chemical correlation to the corresponding known monoacetates, (2S)-(+)-2-acetoxybicycloheptane, (2S)-(+)-2-acetoxybicyclooctane and (2S)-(+)-2-acetoxybicyclooctane, and circular dichroism spectra of keto acetates and diketones derived from the hydrolysis products were examined.