Repozytorium
Wyszukaj
Kolekcje
Inne
Structures of highly twisted amides relevant to amide N—C cross-coupling: evidence for ground-state amide destabilization.
Autorzy
Rok wydania
2016
Czasopismo
Numer woluminu
22
Strony
14494-14498
DOI
10.1002/chem.201603543
Kolekcja
Język
Angielski
Typ publikacji
Artykuł
Herein, we show that acyclic amides that have recently enabled a series of elusive transition-metal-catalyzed N−C activation/cross-coupling reactions are highly twisted around the N−C(O) axis by a new destabilization mechanism of the amide bond. A unique effect of the N-glutarimide substituent, leading to uniformly high twist (ca. 90°) irrespective of the steric effect at the carbon side of the amide bond has been found. This represents the first example of a twisted amide that does not bear significant steric hindrance at the α-carbon atom. The 15N NMR data show linear correlations between electron density at nitrogen and amide bond twist. This study strongly supports the concept of amide bond ground-state twist as a blueprint for activation of amides toward N−C bond cleavage. The new mechanism offers considerable opp
Słowa kluczowe
amides, N−C activation, rotation, steric hindrance, twisted amides
Adres publiczny
http://dx.doi.org/10.1002/chem.201603543
Strona internetowa wydawcy
Podobne publikacje
Palladium-NHC (NHC = N-heterocyclic Carbene)-Catalyzed Suzuki–Miyaura Cross-Coupling of Alkyl Amides.
Wang Chang-An, Rahman Md. Mahbubur, Bisz Elwira, Dziuk Błażej, Szostak Roman, Szostak Michal
Chemistry of bridged lactams: recent developments.
Szostak Roman, Szostak Michal
Electrophilicity scale of activated amides: 17O NMR and 15N NMR chemical shifts of acyclic twisted amides in N−C(O) cross‐coupling.
Ielo Laura, Pace Vittorio, Holzer Wolfgang, Rahman Md. Mahbubur, Meng Guangrong, Szostak Roman, Szostak Michal