title: Nickel-Catalyzed Diaryl Ketone Synthesis by N-C Cleavage: Direct Negishi Cross-Coupling of Primary Amides by Site-Selective N,N-Di-Boc Activation.
abstract: A general Negishi acylation of primary amides enabled by a combination of site-selective N,N-di-Boc activation and nickel catalysis is reported for the first time. The reaction is promoted by a bench-stable, inexpensive Ni catalyst. The reaction shows excellent functional group compatibility, affording functionalized diaryl ketones by selective N-C cleavage. Most notably, this protocol represents the first amide cross-coupling by direct metal insertion of simple and readily available primary amides. The overall strategy by N,N-di-Boc activation/metal insertion is suitable for a broad range of coupling protocols via acylmetals. Mechanistic experiments suggest high reactivity of N,N-di-Boc activated 1° amides in direct amide C-N cross-couplings.
authors.affiliation: Department of Chemistry, Rutgers University , 73 Warren Street, Newark, New Jersey 07102, United States.
authors.forename: Shicheng
authors.initials: S
authors.lastname: Shi
authors.affiliation: Department of Chemistry, Rutgers University , 73 Warren Street, Newark, New Jersey 07102, United States.
authors.forename: Michal
authors.initials: M
authors.lastname: Szostak