Intra-annular cyclophane diamines as proton sponges: a computational study

Gas-phase proton affinities of cyclophanes containing intra-annular amino groups were calculated using density functional theory (DFT) at the B3LYP/6-31+G^∗∗//B3LYP/6-31G^∗ level. They are higher in magnitude as those for proton sponges such as 1,8-bisaminonaphthalene, however, they are slightly weaker bases than 1,8-bis(dimethylamino)naphthalene. The high basicity of the cyclophane diamines is attributed mainly to their structural flexibility, which allows them to maximize the hydrogen bond strength in the cations by achieving N-H?N linearity, while strain relief upon protonation is less important. Another contributing factor is the stabilizing interaction of the added proton with adjacent phenyl π systems of the cyclophanes. Barriers for proton transfer between the nitrogen atoms of the diamine cations are also reported.     

Chemistry of azoimidazoles. Synthesis,spectral characterization and redox studies of N(1)-benzyl-2-(arylazo)imidazolepalladium(II)chloride

Arylazoimidazoles (2) are N,N-chelating ligands. The polymerization trend of the azolate system is restricted via N(1)-benzylation. The parent molecules (2), N(1)-benzylated products (3) and palladium complexes (4) were made by standard methods. The ligands (3) and complexes (4) are new. They have been characterized by elemental analysis, i.r., u.v.-vis. and high resolution 1H-n.m.r. spectral data. Redox studies were carried out by cyclic voltammetry. On complexation, azo reduction is shifted anodically.     

Palladium catalyzed atom-efficient cross-coupling reactions of triarylbismuths with aryl bromides

Aryl bromides (3 equiv) were coupled efficiently with triarylbismuths (1 equiv) in an atom-efficient way using the Pd(OAc)₂/PPh₃ catalytic system in the presence of K₃PO₄ as base in DMF at 90 °C, providing excellent yields of the cross-coupled biaryls in short reaction times.     

Sequential [2+2] Photocycloaddition and Rearrangement to Substituted Cyclopentanone. A formal Synthesis of Planococcyl Acetate

An extremely short synthesis of 2,2-dimethyl-3-hydroxymethyl cyclopentanone 2 (R¹ = R² = Me), an advanced intermediate in the synthesis of the pheromone planococcyl acetate 3, is described.     

Noria: A Highly Xe‐Selective Nanoporous Organic Solid

Separation of xenon and krypton is of industrial and environmental concern; the existing technologies use cryogenic distillation. Thus, a cost‐effective, alternative technology for the separation of Xe and Kr and their capture from air is of significant importance. Herein, we report the selective Xe uptake in a crystalline porous organic oligomeric molecule, noria, and its structural analogue, PgC‐noria, under ambient conditions. The selectivity of noria towards Xe arises from its tailored pore size and small cavities, which allows a directed non‐bonding interaction of Xe atoms with a large number of carbon atoms of the noria molecular wheel in a confined space.     

First Example of Intramolecular C-H Insertion Reaction in an Amino Acid Derived α-Diazoketone

Rh-Catalyzed intramolecular C-H insertion reaction of L-leucine derived α-diazoketone is described.