Sequence-Defined Synthesis Enabled by Fast and Living Anionic Monoaddition of Vinyl Monomers.

The selective monoaddition of polymerizable vinyl monomers like styrenes and methacrylates in a living manner has been achieved for the flash-flow preparation of molecules in a defined sequence with high selectivity. We demonstrated the sequence-defined synthesis of multifunctional molecules using an initiator, functionalized styrenes, diarylethylenes, various methacrylates, and an electrophilic trapping reagent at the living terminus (six-component sequential connection at maximum) without any intermediate purification steps. The anionic living terminus of the vinyl monomers in the flow system described herein is active for polymerization, such that the styrene or methacrylate sequence can be expanded to afford highly dispersed oligomers without affecting other single units, which means that the unequivocal sequences were successfully inserted into the internal or terminal positions. The methodology described herein provides an adaptable method for the construction of new molecular spaces based on unimolecular sequence control and pinpoint functionalization.

Ruthenium-catalysed N-alkylation of anilines with primary carbohydrate alcohols via borrowing hydrogen strategy.

Ruthenium-catalysed N-alkylation of anilines with sugar derivatives proceeded via the borrowing hydrogen strategy. Primary carbohydrate alcohols were successfully applied to N-alkylation of aniline derivatives to give the corresponding aminosugars in high yields.

Electrochemical Epoxidation Catalyzed by Manganese Salen Complex and Carbonate with Boron-Doped Diamond Electrode.

Epoxides are essential precursors for epoxy resins and other chemical products. In this study, we investigated whether electrochemically oxidizing carbonate ions could produce percarbonate to promote an epoxidation reaction in the presence of appropriate metal catalysts, although Tanaka and co-workers had already completed a separate study in which the electrochemical oxidation of chloride ions was used to produce hypochlorite ions for electrochemical epoxidation. We found that epoxides could be obtained from styrene derivatives in the presence of metal complexes, including manganese(III) and oxidovanadium(IV) porphyrin complexes and manganese salen complexes, using a boron-doped diamond as the anode. After considering various complexes as potential catalysts, we found that manganese salen complexes showed better performance in terms of epoxide yield. Furthermore, the substituent effect of the manganese salen complex was also investigated, and it was found that the highest epoxide yields were obtained when Jacobsen's catalyst was used. Although there is still room for improving the yields, this study has shown that the in situ electrochemical generation of percarbonate ions is a promising method for the electrochemical epoxidation of alkenes.