Organolithium Displacement of Aryl Anions from Tertiary Phosphine Derivatives of Diphenyl Ether

Levy, Jack B.; Walton, Richard; Olsen, Ron E.; Symmes, Courtland

doi:10.1080/10426509608545211

Cited by 11 publications

(1 citation statement)

References 5 publications

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“…For the arylation, we employed 2-(trimethylsilyl)ethyl benzyl sulfoxide ( 1a ) and bromobenzene ( 2a ) and examined 44 ligands with Pd(dba) 2 , which was the best palladium source in our diaryl sulfoxide synthesis (see the Supporting Information for details). Among the ligands, SPhos, DCEPhos, DPEPhos, and Cy-CarPhos (see Table for structures) gave the highest assay yields (AY, as determined by HPLC) of benzyl phenyl sulfoxide ( 3a ) on microscale (0.01 mmol). When the ligand screening results were translated to lab scale (0.1 mmol), SPhos resulted in the highest AY ( 1 H NMR) of 3a (47% yield, Table , entry 1).…”

Section: Resultsmentioning

confidence: 99%

Palladium-Catalyzed Arylation of Alkyl Sulfenate Anions

et al. 2015

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A 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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Section: Resultsmentioning

confidence: 99%