Regioselective synthesis of o-triazolyl-1,5-benzodiazepin-2-ones and o-isoxazolyl-1,5-benzodiazepin-2-ones via copper-catalyzed 1,3-dipolar cycloaddition reactions

Abstract

A series of novel O-triazolyl-1,5-benzodiazepin-2-ones 6aeo and O-isoxazolyl-1,5benzodiazepin-2-ones 7aeo was synthesized via a Cu(I)-catalyzed 1,3-dipolar alkyne eazide coupling reaction of N-substituted-1,5-benzodiazepineealkyne derivatives 3aec with various aromatic azides 4aee and nitrile oxides 5aee, respectively. The chemical structures of synthesized compounds were determined using 1 H NMR, 13 C NMR, heteronuclear multiple bond correlation (HMBC), high-resolution mass spectra, as well as elemental analysis and was further confirmed by an X-ray diffraction analysis for compound 7d.

Crystallographic and first‐principles density functional theory study on the structure, noncovalent interactions, and chemical reactivity of 1,5‐benzodiazepin‐2‐ones derivatives

“…Chemical preparations of compounds 1 and 2 have been previously reported by our research group, and X‐ray analysis was only performed to confirm the stereochemistry of the products. Herein, crystalline structures have been fully described based on the SCXRD results.…”

“…All DFT calculations were performed starting from the experimental single‐crystal X‐ray data (crystallographic information files), reported by one of the authors of the present work, as input geometries. The geometry optimizations of different isolated monomer and their dimer models were accomplished in the gas using Gaussian 09, Rev D.01 software package .…”

“…Therefore, the molecular geometries and supramolecular architectures have to be preliminarily evaluated and analyzed for considered starting synthetic derivatives. Likewise, preparation of 4‐(phenylacetate)‐1,5‐benzodiazepin‐2‐one 2 was successfully carried out (Scheme ) . Interestingly, under strictly the same reaction conditions (base, solvent, and temperature), the methylation occurred specifically on the amide moiety, whereas the acylation took place only on the hydroxyl group, an interesting result which has been briefly explained in terms of the hard and soft acids and bases principle .…”

“…Likewise, preparation of 4‐(phenylacetate)‐1,5‐benzodiazepin‐2‐one 2 was successfully carried out (Scheme ) . Interestingly, under strictly the same reaction conditions (base, solvent, and temperature), the methylation occurred specifically on the amide moiety, whereas the acylation took place only on the hydroxyl group, an interesting result which has been briefly explained in terms of the hard and soft acids and bases principle . Due to the fact that structure determines function, the present research was emerged from an attempt to get deeper insights into the structure‐reactivity relationship on 1,5‐benzodiazepin‐2‐ones cyclic class.…”

Recyclable Itaconic Acid with Water as Green Catalytic System: Synthesis of Substituted 1,5‐Benzodiazepine Derivatives at Room Temperature

“…Despite of numerous synthetic methods, most of the reported organic pathways comprise of costly metal catalysts, nano‐composites, harsh catalytic conditions or toxic solvents which makes this protocol as cost ineffective and sluggish. Since, the reaction was already accomplished with various metals like, Ag, Ru, Zn, Bi, Cu, Pb, Au, Nb, Ga, La, Yb, Cd, Sc, Pd etc. including nanomaterials, ionic liquids or other organic promoters.…”