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An efficient chromium(II)-mediated reductive coupling reaction of various CBrF2-containing molecules and aldehydes has been developed. This reaction proceeds presumably via the monofluorinated dichromium(III) intermediate generated by the carbon–fluorine bond activation, and provides a general and straightforward access to synthesize a variety of (E)- or (Z)-β-fluoroallylic alcohols in a highly stereoselective manner. Based on the novel reductive coupling, four types of fluoroalkene dipeptide analogues could be stereoselectively prepared.

We achieved the purification of three alpha-keto ester reductases (Streptomyces avermitilis keto ester reductase, SAKERs-I, -II, and -III) from Streptomyces avermitilis NBRC14893 whole cells. The molecular masses of the native SAKERs-I, -II, and -III were estimated to be 72, 38, and 36 kDa, respectively, by gel filtration chromatography. The subunit molecular masses of SAKERs-I, -II, and -III were also estimated to be 32, 32, and 34 kDa, respectively, by SDS-polyacrylamide gel electrophoresis. The purified SAKERs-II and -III showed a reducing activity for alpha-keto esters (in particular, for ethyl pyruvate). SAKER-I showed a high reducing activity not only toward the alpha- and beta-keto esters, but also toward alpha-keto acid. The N-terminal region amino acid sequences of SAKERs-I, -II, and -III were identical to that of a putative oxidoreductase, SAV2750, a putative oxidoreductase, SAV1849, and a putative oxidoreductase, SAV4117, respectively, hypothetical proteins coded on the S. avermitilis genome.

Co-catalyzed hydrosilylation of β-fluoroalkylated unsaturated ketones (I) affords the hydrosilylated adducts (III) in a highly regio- and stereoselective fashion.

We previously developed antioxidative heat-processed (HP)-koji via two-step heating (55 °C/2days → 75 °C/3 days) of white-koji. In this study, we isolated antioxidants in HP-koji and investigated their formation mechanisms. The antioxidants were identified to be 5-hydroxymethyl furfural (HMF) and 5-(α-D-glucopyranosyloxymethyl)-2-furfural (GMF) based on nuclear magnetic resonance spectral analysis. HMF and GMF were not present in intact koji, but were formed by heating at 75 °C. As production of these antioxidants was more effective by two-step heating than by constant heating at 55 °C or 75 °C, we presumed that the antioxidant precursors are derived enzymatically at 55°C and that the antioxidants are formed subsequently by thermal reaction at 75 °C. The heating assay of saccharide solutions revealed glucose and isomaltose as HMF and GMF precursors, respectively, and thus the novel finding of GMF formation from isomaltose. Finally, HMF and GMF were effectively formed by two-step heating from glucose and isomaltose present in koji.