Influence of the nature of the substituent on the supramolecular synthon in crystals of benzo[b][1,4]diazepine derivatives

Self-Associating Curved π-Electronic Systems with Electron-Donating and Hydrogen-Bonding Properties

“…The electrostatic potentials (ESP) obtained through DFT calculations at the B3LYP/LanL2DZ indicated the higher electron densities at the concave faces than the convex faces particularly for the pyrrole π-planes (Figure a,b­(ii), Figure S37). It is noteworthy that the ESP of 2a exhibited a large difference in electron densities at the concave and convex faces of pyrrole rings compared to those of diphenyl-, difuryl-, and dithienyl-substituted benzodiazepines (Figure S38). The tendencies for the electron density differences between the concave and convex faces have often been observed for molecular tweezers with bent structures bridged by nonconjugated units. , …”

One-pot synthesis of benzo[b][1,4]diazepines via the carbonylative Sonogashira reaction and aza-Michael addition cyclocondensation

“…[20][21][22] Although the synthetic methodology of benzodiazepines has progressed in recent decades, the development of catalytic methods with high step-economy using simply available chemicals still draws significant attention from both academia and the pharmaceutical industry. [23][24][25][26][27][28][29][30][31][32] Our group recently developed a unique N-heterocyclic carbene palladium with triazine wingtips (T-NHC-Pd)-catalysed carbonylation Sonogashira reaction, synthesizing 1,3-ynones with ppm-level catalyst loading. 33 1,3-Ynones as Michael acceptors with versatile reactivity have been demonstrated to be facile synthons for constructing a variety of heterocycles and carbocycles.…”