RESUMEN
The synthesis of a solid, bench-stable, strong organic Brønsted acid with a computed pKa of 0.9 is reported. An X-ray crystal structure and DFT calculations are provided which offer insight into the bonding of this acid. The application of this strong organic Brønsted acid as a catalyst for the intermolecular hydroamination of unactivated alkenes and as an activator for Au(I)-catalyzed alkyne hydroamination with anilines is described.
Asunto(s)
Alquenos/química , Alquinos/química , Aminas/síntesis química , Ácidos Bóricos/química , Oro/química , Aminación , Aminas/química , Compuestos de Anilina/química , Boratos , Ácidos Bóricos/síntesis química , Catálisis , Cristalografía por Rayos X , Concentración de Iones de Hidrógeno , Modelos Moleculares , Estructura Molecular , Teoría CuánticaRESUMEN
The straightforward synthesis of a class of nitrogen-based phase-transfer catalysts (PTCs) having markedly dissociated anions due to interionic donor-donor "ion pair strain" and use for catalyzing benzylation and benzylic fluorination is reported. Provided also is insight into the bonding of disubstituted N- vs so-called divalent carbene-stablized N(I)-centered cations and the unprecedented finding of a cyclopropenium based C-H···πaryl interaction.
RESUMEN
A one-pot synthesis of chiral C(3)-substituted phthalides via an indium-mediated allylation/transesterification reaction is described. The development of this reaction was facilitated through the applied use of DFT calculations to rationalize the stereoselection of a chiral In-mediated process. It was discovered that the enantiomeric excess of this reaction depended upon the steric size, chain length, and substitution of the aldehyde employed.
