The manifold of reaction pathways for the oxidative addition of phenyl bromide and phenyl chloride substrates to phosphine-modified palladium(0) complexes has been investigated with dispersion-corrected density functional theory (B3LYP-D2) for a range of synthetically relevant ligands, permitting the evaluation of ligand, substrate and method effects on calculated predictions. Bulky and electro...

The reactivity of C-CH₃ substituted N-protected aldimines in aza-Henry addition reactions was compared with that of the analogous trifluoromethylated compounds. C-Alkyl aldimines easily reacted with nitro alkanes under solvent-free conditions and in the absence of catalyst, despite being worse electrophiles than C-CF₃ aldimines, they gave the aza-Henry addition only when ZrCl₄ was added. The pr...

The efficacies of many antimicrobial peptides are greatly reduced under high salt concentrations, limiting their development as pharmaceutical compounds. Here, we describe an easy strategy to increase salt resistance of antimicrobial peptides by replacing tryptophan or histidine residues with the bulky amino acids β-naphthylalanine and β-(4,4'-biphenyl)alanine. The activities of the salt-sensit...

The title mol-ecule, C(20)H(31)NO(8), has pseudo-C2 symmetry about the C-N bond, with the bis-(tert-butoxy-carbon-yl)amino group twisted from the benzene ring plane by ca 60° and the bulky tert-butoxy-carbonyl (Boc) groups are orientated away from the substituted aniline group. As part of an anti-bacterial drug discovery programme furnishing analogues of platensimycin, we unexpectedly synthesiz...

The pivotal role played by ω-transaminases (ω-TAs) in the synthesis of chiral amines used as building blocks for drugs and pharmaceuticals is widely recognized. However, bulky are challenging to produce. Herein, a ω-TA (TR8) from marine bacterium was synthesize fluorine amine ketone. An analysis reaction conditions process development showed that isopropylamine concentrations above 75 mM had an...

A bis(resorcinarene) substituted 2,2'-bipyridine was found to bind weakly to small esters like ethyl acetate whereas more bulky esters were not recognized by this hemicarcerand. This size selective molecular recognition could be controlled by a negative cooperative allosteric effect: coordination of a triscarbonyl rhenium chloride fragment to the bipyridine causes a conformational rearrangement...

Addition of bulky primary silanes to the osmium benzyl compound, Cp*(iPr3P)OsCH2Ph, afforded two neutral hydrogen-substituted silylene complexes via activation of two Si-H bonds. These species have been structurally characterized, and their reactivity has been examined experimentally and computationally. Comparison of these neutral silylene complexes with their cationic analogue highlights the ...

Bond-stretch isomerism is predicted not to occur in the parent compound Si4H6 and the substituted 1,3-di-tert-butyl derivative, although the existence of bond-stretch isomerism in the 1,3-dimethyl derivative is a possibility. Bulky bridgehead moieties induce a preference for a short Si−Si bridge bond, while a longer bridge bond length (2.840 Å at the MP2/6-31G(d,p) level) is predicted for the u...