Palladium-Catalyzed Unimolecular Fragment Coupling of N-Allylamides Bearing a Tethered Nucleophile with the Translocation of an Amide Group

Abstract

The palladium-catalyzed reaction of N-allylamides bearing a tethered nucleophile results in the extrusion of an amide moiety in the form of an isocyanate with its subsequent capture by the pendant nucleophile. This reaction involves the net catalytic transposition of an amide group.

Nickel/Photoredox Dual-Catalyzed Conversion of Allyl Esters to Ketones via the Formal Deletion of Oxygen

“…Our group recently reported on the palladium or nickel-catalyzed UFC of amides that proceed via the elimination of isocyanate from an allylic amide . In this Letter, we found that the reaction of allyl amides with a nickel catalyst produces a cationic π-allyl nickel species that contains the corresponding amide anion.…”

Unimolecular Fragment Coupling: A New Bond-Forming Methodology via the Deletion of Atom(s)

“…The overall process can be viewed as a catalytic transposition of an amide group from the middle to the terminal of the molecule (Scheme 23). 130 ■ ELIMINATION OF N 2 FROM 1,2-DIAZENES AND THEIR DERIVATIVES 1,2-Diazenes represent a class of nitrogen-bridged compounds and could be attractive substrates for UFC with the elimination of molecular nitrogen (N 2 ). Indeed, it is well-known that 1,2diazenes can eliminate N 2 by heating at high temperatures or by UV irradiation, which leaves behind carbon-centered radicals that can combine to form C−C bonds, particularly in the case of cyclic 1,2-diazenes (Scheme 24A).…”

“…The overall process can be viewed as a catalytic transposition of an amide group from the middle to the terminal of the molecule ( Scheme 23 ). 130 …”

KOtBu-Catalyzed Synthesis of Isoindole Derivatives from N-Benzyl Amides Bearing an Ortho Alkynyl Group via 1,2-Acyl Shift

“…Our group recently reported on the nickel-catalyzed transformations of amides via the cleavage of the C­(acyl)–N bond . Building upon these studies, we hypothesized that amides bearing an alkynyl group (i.e., 1 ) would undergo cyclization if alkyne-directed oxidative addition of the C­(acyl)–N bond of amides and subsequent alkyne insertion were to occur (Scheme a).…”