TY - JOUR
T1 - Aerobic Linear Allylic C-H Amination
T2 - Overcoming Benzoquinone Inhibition
AU - Pattillo, Christopher C.
AU - Strambeanu, Iulia I.
AU - Calleja, Pilar
AU - Vermeulen, Nicolaas A.
AU - Mizuno, Tomokazu
AU - White, M. Christina
N1 - Publisher Copyright:
© 2016 American Chemical Society.
PY - 2016/2/3
Y1 - 2016/2/3
N2 - An efficient aerobic linear allylic C-H amination reaction is reported under palladium(II)/bis-sulfoxide/Brønsted base catalysis. The reaction operates under preparative, operationally simple conditions (1 equiv of olefin, 1 atm O2 or air) with reduced Pd(II)/bis-sulfoxide catalyst loadings while providing higher turnovers and product yields than systems employing stoichiometric benzoquinone (BQ) as the terminal oxidant. Pd(II)/BQ -acidic interactions have been invoked in various catalytic processes and are often considered beneficial in promoting reductive functionalizations. When such electrophilic activation for functionalization is not needed, however, BQ at high concentrations may compete with crucial ligand (bis-sulfoxide) binding and inhibit catalysis. Kinetic studies reveal an inverse relationship between the reaction rate and the concentration of BQ, suggesting that BQ is acting as a ligand for Pd(II) which results in an inhibitory effect on catalysis.
AB - An efficient aerobic linear allylic C-H amination reaction is reported under palladium(II)/bis-sulfoxide/Brønsted base catalysis. The reaction operates under preparative, operationally simple conditions (1 equiv of olefin, 1 atm O2 or air) with reduced Pd(II)/bis-sulfoxide catalyst loadings while providing higher turnovers and product yields than systems employing stoichiometric benzoquinone (BQ) as the terminal oxidant. Pd(II)/BQ -acidic interactions have been invoked in various catalytic processes and are often considered beneficial in promoting reductive functionalizations. When such electrophilic activation for functionalization is not needed, however, BQ at high concentrations may compete with crucial ligand (bis-sulfoxide) binding and inhibit catalysis. Kinetic studies reveal an inverse relationship between the reaction rate and the concentration of BQ, suggesting that BQ is acting as a ligand for Pd(II) which results in an inhibitory effect on catalysis.
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U2 - 10.1021/jacs.5b11294
DO - 10.1021/jacs.5b11294
M3 - Article
C2 - 26730458
AN - SCOPUS:84957585918
SN - 0002-7863
VL - 138
SP - 1265
EP - 1272
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 4
ER -