Taking the reins : The title transformation of thioamides and N‐diphenylphosphinoyl imines is described. By harnessing the power of cooperative catalysis between a soft Lewis acid and a hard Brønsted base, thioamide carbon pronucleophiles can furnish Mannich products (see scheme). Divergent transformation of the thioamide functionality highlights the utility of this methodology.
Chain change : Variations in the position, number, and chain length of the n‐alkoxy chains readily tune the liquid‐crystalline properties of 2,5‐diaryl‐1,3,4‐thiadiazole derivatives from smectic to hexagonal columnar mesophases at room temperature. The calamitic S‐heterocyclic compounds show electrical conductivity in both solid and liquid‐crystal states.
One catalyst fits all! One catalyst is active for a wide set of benzylating reactions (see scheme). A tandem process allows the use of aldehydes and ketones as benzylating agents.
Roll up : A peptide–dendron hybrid (PDH) is capable of self‐assembling into either a soluble nanotube or an amyloid‐like fibrillar network. The structures interconvert on adjusting the salt concentration or pH value. Their hydrophobic interfaces efficiently encapsulate hydrophobic molecules in water which can then be released by lowering the pH value.
Arene control : Anticancer complexes [Ru(arene)Cl(en)]+ (arene=p‐cymene or biphenyl; en=ethylenediamine) bind to surface histidine (His128, His247, His510) and methionine (Met298) residues in human albumin, but only the p‐cymene complex can gain entry to the crevice containing the free cysteine thiolate (Cys34) and induce oxidation to sulfinate.
Involuntary association : Anionic β‐galactosidase enzymes associate with positively charged Au nanoparticles to produce reduced‐charge conjugates, which assemble at oil–water interfaces to result in stable microcapsules (see picture). The microcapsules were formed quickly and showed high enzymatic activity, which makes them promising materials for biotechnology applications.
An enriching experience : Chiral phosphoric acids have been used to catalyze the title transformation for aromatic and aliphatic hemiaminal ethers. The process affords the corresponding products in good to high enantioselectivity (see scheme; Boc=tert‐butoxycarbonyl, G=aromatic group). The method enables facile access to highly enantioenriched 1,3‐diamine derivatives.
Organolithium chemistry! An overview of the structure formation principles and the strong structure–reactivity relationship of lithium organics is given. By means of the commonly used lithium bases the deaggregation of the oligomeric parent structures to small adducts is presented (see examples) and compared to the related chemistry of lithiosilanes.
Cohesion matters! The correlation between the conformational rigidity of the polyelectrolyte and the size and stability of the globular assembly is discussed in this review article. Some examples of models for the association of polyelectrolytes to globular assemblies are shown here.
Efficient at room temperature : The Au complex generated in situ from [(IPr)AuCl] and AgSbF6 promotes the [4C+3C] intramolecular cycloaddition of allenes and dienes at room temperature, and in a particularly efficient and versatile manner. A DFT study on dimethylallenyl precursors agreed with the formation and cycloaddition of a metal–allyl cation intermediate, and points to the 1,2‐hydride shift as the key rate‐limiting step.
