Efficient access to general α-tertiary amines via water-accelerated organocatalytic multicomponent allylation.

A tetrasubstituted carbon atom connected by three sp3 or sp2-carbons with single nitrogen, i.e., the α-tertiary amine (ATA) functional group, is an essential structure of diverse naturally occurring alkaloids and pharmaceuticals. The synthetic approach toward ATA structures is intricate, therefore, a straightforward catalytic method has remained a substantial challenge. Here we show an efficient water-accelerated organocatalytic method to directly access ATA incorporating homoallylic amine structures by exploiting readily accessible general ketones as useful starting material. The synergistic action of a hydrophobic Brønsted acid in combination with a squaramide hydrogen-bonding donor under aqueous condition enabled the facile formation of the desired moiety. The developed exceptionally mild but powerful system facilitated a broad substrate scope, and enabled efficient multi-gram scalability.

N-Triflyl Phosphoric Triamide: A High-Performance Purely Organic Trifurcate Quartz Crystal Microbalance Sensor for Chemical Warfare Agent.

G-, V-, and A-series nerve agents are extremely toxic organophosphorus chemical warfare agents (CWAs) that incorporate P═O functional groups. Their colorless, tasteless, and odorless nature makes rapid and efficient detection challenging. Here, we report an unprecedented N-triflyl phosphoric triamide (N-TPT) receptor, which is a new class of triple hydrogen bonding donor molecular sensors for CWA recognition via noncovalent host-guest-type interactions. The highly robust trifurcate structures were designed based on density functional theory (DFT) computations and synthesized from N-triflyl phosphorimidoyl trichloride by simple stepwise processes. Quartz crystal microbalance (QCM) analysis allowed robust detection of typical CWA simulants, such as dimethyl methylphosphonate. The concentration-dependent QCM profiles were fitted with the Sips isotherm model, revealing that the thermodynamic parameters of the binding behaviors are roughly correlated with the calculated results. Developed N-TPT receptors show higher binding abilities than previously reported receptors and reasonable selectivity over other volatile compounds.