title: Palladium-Catalyzed Suzuki-Miyaura Coupling of Aryl Esters.
abstract: The Suzuki-Miyaura coupling is among the most important C-C bond-forming reactions available due to its reliability, chemoselectivity, and diversity. Aryl halides and pseudohalides such as iodides, bromides, and triflates are traditionally used as the electrophilic coupling partner. The expansion of the reaction scope to nontraditional electrophiles is an ongoing challenge to enable an even greater number of useful products to be made from simple starting materials. Herein, we present how an NHC-based Pd catalyst can enable Suzuki-Miyaura coupling where the C(acyl)-O bond of aryl esters takes on the role of electrophile, allowing the synthesis of various ketone-containing products. This contrasts known reactions of similar esters that provide biaryls via nickel catalysis. The underlying cause of this mechanistic divergence is investigated by DFT calculations, and the robustness of esters compared to more electrophilic acylative coupling partners is analyzed.
authors.affiliation: Centre for Catalysis Research and Innovation, Department of Chemistry and Biomolecular Sciences, University of Ottawa , 10 Marie Curie, Ottawa, Ontario K1N 6N5, Canada.
authors.forename: Taoufik
authors.initials: T
authors.lastname: Ben Halima
authors.affiliation: Centre for Catalysis Research and Innovation, Department of Chemistry and Biomolecular Sciences, University of Ottawa , 10 Marie Curie, Ottawa, Ontario K1N 6N5, Canada.
authors.forename: Wanying
authors.initials: W
authors.lastname: Zhang
authors.affiliation: Centre for Catalysis Research and Innovation, Department of Chemistry and Biomolecular Sciences, University of Ottawa , 10 Marie Curie, Ottawa, Ontario K1N 6N5, Canada.
authors.forename: Imane
authors.initials: I
authors.lastname: Yalaoui
authors.affiliation: Department of Chemistry, Zhejiang University , Hangzhou 310027, China.
authors.forename: Xin
authors.initials: X
authors.lastname: Hong
authors.affiliation: Department of Chemistry and Biochemistry, University of California , Los Angeles, California 90095, United States.
authors.forename: Yun-Fang
authors.identifier: 0000-0002-6287-1640
authors.initials: YF
authors.lastname: Yang
authors.affiliation: Department of Chemistry and Biochemistry, University of California , Los Angeles, California 90095, United States.
authors.forename: Kendall N
authors.initials: KN
authors.lastname: Houk
authors.affiliation: Centre for Catalysis Research and Innovation, Department of Chemistry and Biomolecular Sciences, University of Ottawa , 10 Marie Curie, Ottawa, Ontario K1N 6N5, Canada.
authors.forename: Stephen G
authors.identifier: 0000-0003-1949-5069
authors.initials: SG
authors.lastname: Newman