Computational and experimental investigation on the BCl promoted intramolecular amination of alkenes and alkynes.

The BX3 promoted transition-metal-free borylative cyclizations have recently attracted increasing attention. In 2015, the Li group reported a BCl3 mediated aminoboration of unfunctionalized olefins. In their originally proposed reaction pathways, the overall reaction barrier was calculated to be about 35 kcal mol-1, which is too high to be reasonable for a reaction that smoothly occurs at room temperature.

A combined experimental and DFT mechanistic study for the unexpected nitrosolysis of -hydroxymethyldialkylamines in fuming nitric acid.

The reaction of dimorpholinomethane in fuming HNO was investigated. Interestingly, the major product was identified as -nitrosomorpholine and a key intermediate -hydroxymethylmorpholine was detected during the reaction by H-NMR tracking which indicates that the reaction proceeds an unexpected nitrosolysis process. A plausible nitrosolysis mechanism for -hydroxymethyldialkylamine in fuming nitric acid involving a HNO redox reaction is proposed, which is supported by both experimental results and density functional theory (DFT) calculations.