We report a route to benzosultams that exploits the palladium-catalysed aminsulfonylation of alkenyl iodides as initial step. An (Z)-configured iodide substrate is combined with DABSO, N,N-dialkylhydrazine nucleophile and palladium(0) catalyst achieve aminsulfonylation. A second palladium(0)-catalysed transformation, this time intramolecular, leads benzosultam formation. Good variation starting...

A unique anionic phosphenium complex was prepared from reaction of an N-heterocyclic chlorophosphine with Collman's reagent or K[HFe(CO)4]/NaH and characterized by spectral and XRD data. The complex behaves as an ambident nucleophile. Reactions with acetic acid, ClSnPh3, and a further equivalent of an N-heterocyclic chlorophosphine proceed via electrophilic functionalization at the metal site t...

The synthesis of dibenzyl-(1S*,2S*)-2,3-dihydro-1H-indene-1,2-dicarboxylate has been realized through a diastereospecific bis-alkoxycarbonylation reaction, which starts from the cheap and easily available 1H-indene, benzyl alcohol, carbon monoxide. catalyst is formed in situ by mixing Pd(TFA)2, ligand N2,N3-bis(2,6-dimethylphenyl)butane-2,3-diimine, p-benzoquinone used as an oxidant, alcohol ac...

Multi-electrophilic yet compact, the rigid α-methylene-β-lactone (MeLac) warhead creates new opportunities to probe live-cell proteome. The MeLac reacts with five types of nucleophile on all seven classes enzymes. Protein structures show reacting residues in red and blue. On upper left, a protein directs tethering an affinity ligand (yellow) probe. More information can be found full paper by X....

Rate constants for the reactions of substituted quinuclidines with pnitrophenyl phosphate, 2,4-dinitrophenyl phosphate, 2,4-dinitrophenyl phosphate complexed with calcium, and phosphorylated pyridine decrease with increasing pKa of the amine. Plots of log k against pK, give slopes of @ , , = -0.05, -0.10, -0.1 1, and 4.10, respectively, for these.compounds; &, = -0.01 for phosphorylated 4-morph...

DeazaFMN-containing glycolate oxidase has been prepared and shown to catalyze the stereospecific transfer of the alpha-hydrogen from substrate to enzyme-bound deazaFMN. The reaction of sulfite, cyanide, and hydroxylamine with several deazaflavin-containing enzymes (glycolate oxidase, D-amino acid oxidase, glucose oxidase, N-methylglutamate synthetase) and free deazaFMN has been examined. All th...

where k is the rate constant for a reaction of an electrophile with a given nucleophilic system, k 0 is dependent solely on the identity of the electrophile and N + is a parameter characteristic of the nucleophilic system. The most surprising result of this relation is its incompatibility with the reactivity-selectivity principle, because, since N + is independent of the electrophile, the relat...