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Modular Functionalization of Arenes in a Triply Selective Sequence: Rapid C(sp2) and C(sp3) Coupling of C-Br, C-OTf, and C-Cl Bonds Enabled by a Single Palladium(I) Dimer

Journal Article


Abstract


  • Full control over multiple competing coupling sites would enable straightforward access to densely functionalized compound libraries. Historically, the site selection in Pd0-catalyzed functionalizations of poly(pseudo)halogenated arenes has been unpredictable, being dependent on the employed catalyst, the reaction conditions, and the substrate itself. Building on our previous report of C−Br-selective functionalization in the presence of C−OTf and C−Cl bonds, we herein complete the sequence and demonstrate the first general arylations and alkylations of C−OTf bonds (in <10 min), followed by functionalization of the C−Cl site (in <25 min), at room temperature using the same air- and moisture-stable PdI dimer. This allowed the realization of the first general and triply selective sequential C−C coupling (in 2D and 3D space) of C−Br followed by C−OTf and then C−Cl bonds.

Publication Date


  • 2018

Citation


  • Keaveney, S. T., Kundu, G., & Schoenebeck, F. (2018). Modular Functionalization of Arenes in a Triply Selective Sequence: Rapid C(sp2) and C(sp3) Coupling of C-Br, C-OTf, and C-Cl Bonds Enabled by a Single Palladium(I) Dimer. Angewandte Chemie - International Edition, 57(38), 12573-12577. doi:10.1002/anie.201808386

Scopus Eid


  • 2-s2.0-85053034370

Start Page


  • 12573

End Page


  • 12577

Volume


  • 57

Issue


  • 38

Abstract


  • Full control over multiple competing coupling sites would enable straightforward access to densely functionalized compound libraries. Historically, the site selection in Pd0-catalyzed functionalizations of poly(pseudo)halogenated arenes has been unpredictable, being dependent on the employed catalyst, the reaction conditions, and the substrate itself. Building on our previous report of C−Br-selective functionalization in the presence of C−OTf and C−Cl bonds, we herein complete the sequence and demonstrate the first general arylations and alkylations of C−OTf bonds (in <10 min), followed by functionalization of the C−Cl site (in <25 min), at room temperature using the same air- and moisture-stable PdI dimer. This allowed the realization of the first general and triply selective sequential C−C coupling (in 2D and 3D space) of C−Br followed by C−OTf and then C−Cl bonds.

Publication Date


  • 2018

Citation


  • Keaveney, S. T., Kundu, G., & Schoenebeck, F. (2018). Modular Functionalization of Arenes in a Triply Selective Sequence: Rapid C(sp2) and C(sp3) Coupling of C-Br, C-OTf, and C-Cl Bonds Enabled by a Single Palladium(I) Dimer. Angewandte Chemie - International Edition, 57(38), 12573-12577. doi:10.1002/anie.201808386

Scopus Eid


  • 2-s2.0-85053034370

Start Page


  • 12573

End Page


  • 12577

Volume


  • 57

Issue


  • 38