title: Palladium-Catalyzed Arylation of Alkyl Sulfenate Anions.
abstract: 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.
authors.affiliation: Roy and Diana Vagelos Laboratories, Penn/Merck Laboratory for High-Throughput Experimentation, Department of Chemistry, University of Pennsylvania , 231 S. 34th St., Philadelphia, Pennsylvania 19104-6323, United States.
authors.forename: Tiezheng
authors.initials: T
authors.lastname: Jia
authors.affiliation: Roy and Diana Vagelos Laboratories, Penn/Merck Laboratory for High-Throughput Experimentation, Department of Chemistry, University of Pennsylvania , 231 S. 34th St., Philadelphia, Pennsylvania 19104-6323, United States.
authors.forename: Mengnan
authors.initials: M
authors.lastname: Zhang
authors.affiliation: Roy and Diana Vagelos Laboratories, Penn/Merck Laboratory for High-Throughput Experimentation, Department of Chemistry, University of Pennsylvania , 231 S. 34th St., Philadelphia, Pennsylvania 19104-6323, United States.
authors.forename: Hui
authors.initials: H
authors.lastname: Jiang
authors.affiliation: Roy and Diana Vagelos Laboratories, Penn/Merck Laboratory for High-Throughput Experimentation, Department of Chemistry, University of Pennsylvania , 231 S. 34th St., Philadelphia, Pennsylvania 19104-6323, United States.
authors.forename: Carol Y
authors.initials: CY
authors.lastname: Wang
authors.affiliation: Roy and Diana Vagelos Laboratories, Penn/Merck Laboratory for High-Throughput Experimentation, Department of Chemistry, University of Pennsylvania , 231 S. 34th St., Philadelphia, Pennsylvania 19104-6323, United States.
authors.forename: Patrick J
authors.initials: PJ
authors.lastname: Walsh