Synthesis of α-(4-Oxazolyl)amino Esters via Brønsted Acid Catalyzed Tandem Reaction.

A one-step, Brønsted acid catalyzed tandem reaction for the synthesis of α-(4-oxazolyl)amino esters was developed. 4-Nitrobenzenesulfonic acid was found to be an efficient catalyst for the coupling of ethyl 2-oxobut-3-ynoates with amides to provide various α-(4-oxazolyl)amino esters. The experimental and X-ray crystallographic data suggest that a series of bond-forming reactions including imine formation, intermolecular Michael addition, and intramolecular Michael addition are involved to generate both the oxazole and amino acid functionalities.

Alkoxide Migration at a Nickel(II) Center Induced by a π-Acidic Ligand: Migratory Insertion versus Metal-Ligand Cooperation.

Two pathways of alkoxide migration occurring at a nickel(II) center supported by a PPP ligand (PPP = P[2-PPr-CH]) are presented in this Article. In the first route, the addition of a π-acidic ligand to a (PPP)Ni alkoxide species reveals the formation of a P-O bond. This reaction occurs via metal-ligand cooperation (MLC) involving a 2-electron reduction at nickel.

Phosphinite-Ni(0) mediated formation of a phosphide-Ni(II)-OCOOMe species via uncommon metal-ligand cooperation.

Reversible transformations are observed between a phosphide-nickel(II) alkoxide and a phosphinite-nickel(0) species via a P-O bond formation coupled with a 2-e(-) redox change at the nickel center. In the forward reaction, the nickel(0) dinitrogen species (PP(OMe)P)Ni(N2) (2) and {(PP(OMe)P)Ni}2(μ-N2) (3) were formed from the reaction of (PPP)NiCl (1) with a methoxy anion. In the backward reaction, a (PPP)Ni(II) moiety was regenerated from the CO2 reaction of 3 with the concomitant formation of a methyl carbonate ligand in (PPP)Ni(OCOOMe) (7).