Metal-ion complexes are the most effective artificial catalysts capable of cleaving phosphate diesters under mild aqueous conditions. A central strategy for making these complexes highly reactive has been to use ligand-based alcohols that are coordinated to the ion, providing an ionised nucleophile under neutral conditions but at the expense of deactivating it. We have created a highly reactive...

A method for the rapid modification under mild conditions of carboxyl groups in proteins has been developed. The method involves the activation of the carboxyl group by a water-soluble carbodiimide and the subsequent reaction of the activated carboxyl group with a nucleophile such as glycine methyl ester. The kinetics of the reaction indicates that there are limits to the variation of carbodiim...

A previously determined crystal structure of the ternary complex of trehalose-6-phosphate synthase identified a putative transition state-like arrangement based on validoxylamine A 6'-O-phosphate and uridine diphosphate in the active site. Here linear free energy relationships confirm that these inhibitors are synergistic transition state mimics, supporting front-face nucleophilic attack involv...

•Unified solution to decarboxylative cross-nucleophile coupling reactions•Photoactive Fe(III) carboxylates + Fe(III)-mediated oxidation•Fe(III) salts are non-toxic, earth abundant, and low cost•Direct formation of C–C, C–O, C–S, C–N bonds without prefunctionalization Carboxylic acids valuable chemical building blocks because they widely available with significant structural diversity. Decarboxy...

Glycosylasparaginase (GA) is a member of a novel family of N-terminal nucleophile hydrolases that catalytically use an N-terminal residue as both a polarizing base and a nucleophile. These enzymes are activated from a single chain precursor by intramolecular autoproteolysis to yield the N-terminal nucleophile. A deficiency of GA results in the human genetic disorder known as aspartylglycosaminu...

Aspartylglucosaminidase (AGA) belongs to the N-terminal nucleophile (Ntn) hydrolase superfamily characterized by an N-terminal nucleophile as the catalytic residue. Three-dimensional structures of the Ntn hydrolases reveal a common folding pattern and equivalent stereochemistry at the active site. The activation of the precursor polypeptide occurs autocatalytically, and for some amidohydrolases...

Due to the importance and various applications of nitriles especially in medicinal productions, a new method for conversion of aldehydes to nitriles has been presented. Several nitrile-containing aromatic compounds were synthesized through the treatment of various aldehydes and hydroxylamine hydrochloride as nucleophile in the presence of ferric hydrogen sulfate as a heterogeneous, efficient, a...