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Modular Functionalization of Arenes in a Triply Selective Sequence: Rapid C(sp 2 ) and C(sp 3 ) Coupling of C−Br, C−OTf, and C−Cl Bonds Enabled by a Single Palladium(I) Dimer
Author(s) -
Keaveney Sinead T.,
Kundu Gourab,
Schoenebeck Franziska
Publication year - 2018
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201808386
Subject(s) - surface modification , chemistry , catalysis , substrate (aquarium) , dimer , stereochemistry , sequence (biology) , coupling (piping) , combinatorial chemistry , crystallography , organic chemistry , materials science , biochemistry , oceanography , geology , metallurgy
Full control over multiple competing coupling sites would enable straightforward access to densely functionalized compound libraries. Historically, the site selection in Pd 0 ‐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 Pd I 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.