Chan–Evans–Lam Couplings with Copper
Iminoarylsulfonate Complexes: Scope and Mechanism
Version 2 2018-07-15, 12:04
Version 1 2018-07-15, 12:03
Posted on 2018-07-15 - 12:04
Copper(II)
pyridyliminoarylsulfonate complexes with chloride or
triflate counteranions were employed in Chan–Evans–Lam
(CEL) couplings of N-nucleophiles and arylboronic acids. The complexes
avoided typical side reactions in CEL couplings, and an excess of
boronic acid was not required. Water was tolerated, and addition of
neither base nor other additives was necessary. Primary amines, acyclic
and cyclic secondary amines, anilines, aminophenol, imidazole, pyrazole,
and phenyltetrazole can be quantitatively arylated at either 25 or
50 °C with 2.5 mol % of the catalyst. Reaction kinetics were
investigated in detail. Kinetic and spectroscopic studies provide
evidence for the formation of unproductive copper–substrate
complexes. Formation of an aniline–phenylboronic acid adduct
was responsible for the zero-order dependence of reaction rates on
phenylboronic acid concentration. Kinetic evidence indicates that
the order of reaction steps is transmetalation, nucleophile coordination,
and oxidation. Couplings performed poorly with electron-deficient
arylboronic acids, due to a slower Cu(II)/Cu(III) oxidation in the
catalytic cycle. Photoredox catalysis partially resolved this problem,
but addition of copper acetate as an external oxidant proved to be
more efficient.
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Hardouin Duparc, Valérie; Bano, Guillaume L.; Schaper, Frank (2018). Chan–Evans–Lam Couplings with Copper
Iminoarylsulfonate Complexes: Scope and Mechanism. ACS Publications. Collection. https://doi.org/10.1021/acscatal.8b01881
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AUTHORS (3)
VH
Valérie Hardouin Duparc
GB
Guillaume L. Bano
FS
Frank Schaper
KEYWORDS
reaction ratesPhotoredox catalysisKinetic evidencespectroscopic studiesCopper Iminoarylsulfonate Complexesarylboronic acidscopper acetateelectron-deficient arylboronic acidsoxidationside reactionsformationreaction stepsChantriflate counteranionsnucleophile coordinationReaction kineticsCEL couplingsPrimary aminesboronic acidphenylboronic acid concentrationzero-order dependenceanilineCouplingcomplex