Ar eactioni nvolving ortho-aminomethylation of phenolw as developed via ruthenium-catalyzed dehydrogenation of methanol, an environmentally benign C 1 building block, without the use of reactive reagents.T he reactionw as successfully applied to ar ange of substrates.W hen naphthol was employed insteado fp henol, only methylationw as observed. On the basis of various mechanistics tudies, we propose that formamide barely participates in the reaction, which mainly occurs through an iminium cation intermediate.T he difference in the reactivities of phenoland naphthol is attributable to stronger basicity of naphtholate as ac onjugate base owingt oi ts lower aromaticity. Plausible reactionp athways were proposedfor both reactions.

An ovel synthetic protocol for N-aryl-b-enaminonitriles,w hich are useful building blocks for heterocycle synthesis, was developed using isocyanides as the nitrogen source.U sing copper-catalyzed one-stepr eactions between isocyanides and benzyl cyanidesu nder mild conditions,d iverse N-aryl-b-enaminonitriles could be synthesizedi ne xcellent yields and with high atom-efficiency. N-Alkyl-b-enaminonitriles were also synthesizedi ng ood yields. Am echanism involving an imidoyl-copper intermediate was proposedb ased on mechanistic studies and previous reports. In addition,w ed emonstrated that as ynthesized N-aryl-b-enaminonitrile could be utilized for the synthesiso fab -keto nitrile compound and3 -aminopyrazole.

A organocatalytic system based on economical and readily available cyanuric acid has been developed for the synthesis of 2-oxazolidinones and quinazoline-2,4(1H,3H)-diones from propargylamines and 2-aminobenzonitriles under atmospheric pressure carbon dioxide. Notably, a low concentration of carbon dioxide in air was directly converted into 2-oxazolidinone in excellent yields without an external base. Through mechanistic investigation by in situ FTIR spectroscopy, cyanuric acid was demonstrated to be an efficient catalyst for carbon dioxide fixation.

Atom-economical C–C coupling between imines and a C1 source could provide α-aminoaldehyde derivatives. Nevertheless, such a coupling has rarely been achieved owing to the lack of appropriate nucleophilic C1 sources. In this study, photocatalytic synthesis of α-aminoacetals was achieved via decarboxylative coupling of imine and 2,2-diethoxyacetic acid using a nonstoichiometric amount of a radical initiator. Various functional groups were compatible, providing efficient one-step access to diversely functionalized α-aminoacetals, which provides a promising platform for further research.

No abstract