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Selective ortho ‐Functionalization of Adamantylarenes Enabled by Dispersion and an Air‐Stable Palladium(I) Dimer
Author(s) -
Kalvet Indrek,
Deckers Kristina,
FunesArdoiz Ignacio,
Magnin Guillaume,
Sperger Theresa,
Kremer Marius,
Schoenebeck Franziska
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202001326
Subject(s) - steric effects , palladium , dimer , chemistry , surface modification , alkylation , dispersion (optics) , catalysis , combinatorial chemistry , stereochemistry , organic chemistry , physics , optics
Contrary to the general belief that Pd‐catalyzed cross‐coupling at sites of severe steric hindrance are disfavored, we herein show that the oxidative addition to C−Br ortho to an adamantyl group is as favored as the corresponding adamantyl‐free system due to attractive dispersion forces. This enabled the development of a fully selective arylation and alkylation of C−Br ortho to an adamantyl group, even if challenged with competing non‐hindered C−OTf or C−Cl sites. The method makes use of an air‐stable Pd I dimer and enables straightforward access to diversely substituted therapeutically important adamantylarenes in 5–30 min.