A Palladium(II)‐Catalyzed C?H Activation Cascade Sequence for Polyheterocycle Formation

Polyheterocycles are found in many natural products and are useful moieties in functional materials and drug design. As part of a program towards the synthesis of Stemona alkaloids, a novel palladium(II)‐catalyzed C H activation strategy for the construction of such systems has been developed. Starting from simple 1,3‐dienyl‐substituted heterocycles, a large range of polycyclic systems containing pyrrole, indole, furan and thiophene moieties can be synthesized in a single step.     

A Single Enzyme Transforms a Carboxylic Acid into a Nitrile through an Amide Intermediate

The biosynthesis of nitriles is known to occur through specialized pathways involving multiple enzymes; however, in bacterial and archeal biosynthesis of 7‐deazapurines, a single enzyme, ToyM, catalyzes the conversion of the carboxylic acid containing 7‐carboxy‐7‐deazaguanine (CDG) into its corresponding nitrile, 7‐cyano‐7‐deazaguanine (preQ₀). The mechanism of this unusual direct transformation was shown to proceed via the adenylation of CDG, which activates it to form the newly discovered amide intermediate 7‐amido‐7‐deazaguanine (ADG). This is subsequently dehydrated to form the nitrile in a process that consumes a second equivalent of ATP. The authentic amide intermediate is shown to be chemically and kinetically competent. The ability of ToyM to activate two different substrates, an acid and an amide, accounts for this unprecedented one‐enzyme catalysis of nitrile synthesis, and the differential rates of these two half reactions suggest that this catalytic ability is derived from an amide synthetase that gained a new function.     

Kerr effect in the isotropic melt of smectic polymer

Electric birefringence in the isotropic melt of a comb-like polyacrylate with mesogenic cyanobiphenyl side groups has been studied. A fraction with the degree of polymerization 200, which forms a smectic mesophase, has been considered. The change in the character of the temperature dependence of the Kerr constant has been revealed in the isotropic phase above the smectic–isotropic phase transition temperature. This effect is explained by the change in the character of short-range order in the isotropic–isotropic phase transition.     

Sorption and Separation of Optical Isomers of 2-Butanol by Chiral Porous Coordination Polymers

Theoretical and Experimental Chemistry - It was shown that porous coordination polymers (PCPs) of 3d metals containing chiral centers in fragments of deprotonated (S)-lactic and (R)-aspartic acid...