Published in Chemical science
We outline a strategy to enable non-directed Pd(II)-catalyzed C-H functionalization in the presence of Lewis basic heterocycles. In a high-throughput screen of two Pd-catalyzed C-H acetoxylation reactions, addition of a variety of N-containing heterocycles is found to cause low product conversion. A pyridine-containing test substrate is selected as...
Published in Journal of the American Chemical Society
Predicting site selectivity in C-H bond oxidation reactions involving heteroatom transfer is challenged by the small energetic differences between disparate bond types and the subtle interplay of steric and electronic effects that influence reactivity. Herein, the factors governing selective Rh2(esp)2-catalyzed C-H amination of isoamylbenzene deriv...
Published in Angewandte Chemie International Edition in English
A Robinson annulation, van Leusen homologation, and a desymmetrizing C-H oxidation enabled an enantiospecific synthesis of the neurotrophic natural product jiadifenolide. From a pulegone-derived building block, a key propellane intermediate was constructed through the use of simple reagents in a highly diastereoselective fashion. A short series of ...
Published in Advances in Chemical Engineering and Science
Selective hydroxylation of 3° and benzylic C–H bonds is made possible using a non-metal-based catalyst system, Oxone as the terminal oxidant, and an aqueous fluoroalcohol solvent mixture. The choice of solvent is uniquely effective for this process, but seemingly at odds with our finding that H2O promotes reduction of the oxaziridine intermediate. ...
Published in Journal of the American Chemical Society
The synthesis of 1,2-diamines has been achieved through a single-step, tandem sequence involving Rh-catalyzed aziridination followed by NaI-promoted rearrangement to an isomeric cyclic sulfamide. Facile ring opening of these products in hot water and pyridine affords differentially protected vicinal diamines. Demonstration of the utility of this me...
Published in The Journal of Organic Chemistry
A versatile strategy for C7-selective boronation of tryptophans, tryptamines, and 3-alkylindoles by way of a single-pot C2/C7-diboronation–C2-protodeboronation sequence is described. The combination of a mild iridium-catalyzed C2/C7-diboronation followed by an in situ palladium-catalyzed C2-protodeboronation allows efficient entry to valuable C7-bo...
Published in Advances in Chemical Engineering and Science
Mechanistic insight into a C–H hydroxylation reaction catalysed by [(Me3tacn)RuCl3] has been obtained using desorption electrospray ionization mass spectrometry (DESI-MS) to identify reactive intermediates and to determine the fate of the starting metal complex. Our studies provide direct evidence for the formation of a high-valent dioxo-Ru(VI) spe...
Published in Chem-Bio Informatics Journal
As good as the real thing: Strain‐promoted azide–alkyne cycloaddition can be used to generate artificial metalloenzymes (ArMs) from scaffold proteins containing a p‐azido‐L‐phenylalanine (Az) residue and catalytically active bicyclononyne‐linked cofactors. This method showed broad scope with respect to both the scaffold and cofactor components, and...
Published in ACS Catalysis
Published in Journal of the American Chemical Society
