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Download filePalladium-Catalyzed Arylation of Alkyl Sulfenate Anions
journal contribution
posted on 2015-11-04, 00:00 authored by Tiezheng Jia, Mengnan Zhang, Hui Jiang, Carol Y. Wang, Patrick J. WalshA unique
palladium-catalyzed arylation of alkyl sulfenate anions
is introduced that affords aryl alkyl sulfoxides in high yields. Due
to the base sensitivity of the starting sulfoxides, sulfenate anion
intermediates, and alkyl aryl sulfoxide products, the use of a mild
method to generate alkyl sulfenate anions was crucial to the success
of this process. Thus, a fluoride triggered elimination strategy was
employed with alkyl 2-(trimethylsilyl)ethyl sulfoxides to liberate
the requisite alkyl sulfenate anion intermediates. In the presence
of palladium catalysts with bulky monodentate phosphines (SPhos and
Cy-CarPhos) and aryl bromides or chlorides, alkyl sulfenate anions
were readily arylated. Moreover, the thermal fragmentation and the
base promoted elimination of alkyl sulfoxides was overridden. The
alkyl sulfenate anion arylation exhibited excellent chemoselectivity
in the presence of functional groups, such as anilines and phenols,
which are also known to undergo palladium catalyzed arylation reactions.
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Keywords
alkyl aryl sulfoxide productsalkyl sulfenate anionsalkyl sulfenate anion intermediatesmonodentate phosphinesbase sensitivitysulfenate anion intermediatesaryl alkyl sulfoxidesalkyl sulfoxidespalladium catalystsalkyl sulfenate anion arylationelimination strategyarylation reactionsaryl bromidesAlkyl Sulfenate AnionsA