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Inne
Pd-induced double C—H bond activation in annulative syntheses of bipyrrole boomerangs: mechanistic insights from NMR spectroscopy and computation.
Autorzy
Rok wydania
2018
Czasopismo
Numer woluminu
83
Strony
5199-5209
DOI
10.1021/acs.joc.8b00630
Kolekcja
Język
Angielski
Typ publikacji
Artykuł
1, n-Dipyrrolylalkanes can be efficiently converted into extensively π-conjugated bipyrroles by PdII-mediated annulative double C-H activation, and this approach might be further developed into tandem processes involving further cyclization of substituents or oxygenation of pyrrolic α-positions. Herein, the mechanism of these transformations is explored using NMR spectroscopy and DFT calculations. The kinetics of the annulation are found to depend on the conjugation extent and donor-acceptor character of the pyrroles, as well as on substitution and the linker length. Combined experimental and theoretical evidence indicates that a change of the rate-determining step occurs for the most electron-deficient substrates. The unprecedented double α-oxygenation of bipyrroles is found to be a stepwise process, involving α-acetoxylated intermediates.
Adres publiczny
https://doi.org/10.1021/acs.joc.8b00630