Hydrazine-Halogen Exchange Strategy Toward NâN-Containing Compounds and Process Tracking for Mechanistic Insight.
Org Lett
; 25(14): 2415-2419, 2023 Apr 14.
Article
in En
| MEDLINE
| ID: mdl-37014715
ABSTRACT
An anhydride-promoted traceless hydrazine-I/Br exchange strategy is reported, where hydrazine hydrate and cyclic/linear iodonium, including rarely explored cyclic bromonium, are converted to benzo[c]cinnolines/azobenzenes in one pot. The reaction proceeds through diacylation (first and second CâN formation), N,N'-diarylation (third and fourth CâN formation), and deacylation/oxidation (2 CâN cleavages and 1 NâN formation). The reaction mechanism is investigated by isolating multiple intermediates and kinetic studies. Furthermore, time-dependent electrospray ionization mass spectrometry (TD ESI-MS) was applied to track the process by detecting most intermediates. The complex [CuIII(iodobiphenyl)(bipy)I]+ (Int-C) was detected for the first time, giving evidence for oxidative addition of cyclic iodonium to Cu catalyst. Another complex [CuI(PHA)(bipy)] (Int-B) via ligand-exchange between the hydrazide and Cu catalyst was also detected, indicating a two-path initial activation process.
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Language:
En
Journal:
Org Lett
Journal subject:
BIOQUIMICA
Year:
2023
Document type:
Article
Affiliation country:
China