Catalytic C–S,
C–Se, and C–P
Cross-Coupling Reactions Mediated by a Cu<sup>I</sup>/Cu<sup>III</sup> Redox Cycle
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Abstract
A well-defined macrocyclic aryl-Cu<sup>III</sup> complex
(<b>1</b>) readily reacts with a series of R–SH, Ar–SH,
Ar–SeH, and (RO)<sub>2</sub>(O)–PH (R = alkyl) nucleophiles
to quantitatively afford the corresponding aryl alkyl thioethers,
biaryl thioethers, biaryl selenide, and aryl dialkyl phosphonates,
respectively. Competition experiments using bifunctional substrates
revealed the important impact of lower p<i>K</i><sub>a</sub> values in order to discriminate between functional groups, although
other influencing parameters such as steric effects have been identified.
The catalytic version of these reactions is achieved using aryl bromide
and aryl chloride model substrates, affording C–S, C–Se,
and C–P coupling compounds in excellent to moderate yields.
Low-temperature UV–vis and NMR monitoring of the reactions
of complex <b>1</b> with a variety of nucleophiles support the
formation of a ground-state <b>1</b>–nucleophile adduct.
A mechanistic proposal for reaction of <b>1</b> with S-nucleophiles
involving key nucleophile deprotonation and aryl-nucleophile reductive
elimination steps is finally described