title: Ground-State Distortion in N-Acyl-tert-butyl-carbamates (Boc) and N-Acyl-tosylamides (Ts): Twisted Amides of Relevance to Amide N-C Cross-Coupling.
abstract: Amide N-C(O) bonds are generally unreactive in cross-coupling reactions employing low-valent transition metals due to nN → π*C═O resonance. Herein we demonstrate that N-acyl-tert-butyl-carbamates (Boc) and N-acyl-tosylamides (Ts), two classes of acyclic amides that have recently enabled the development of elusive amide bond N-C cross-coupling reactions with organometallic reagents, are intrinsically twisted around the N-C(O) axis. The data have important implications for the design of new amide cross-coupling reactions with the N-C(O) amide bond cleavage as a key step.
authors.affiliation: Department of Chemistry, Wroclaw University , F. Joliot-Curie 14, Wroclaw 50-383, Poland.
authors.forename: Roman
authors.initials: R
authors.lastname: Szostak
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: Guangrong
authors.initials: G
authors.lastname: Meng
authors.affiliation: Department of Chemistry, Rutgers University , 73 Warren Street, Newark, New Jersey 07102, United States.
authors.forename: Roger
authors.initials: R
authors.lastname: Lalancette
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