Selective ortho-Functionalization of Adamantylarenes Enabled by Dispersion and an Air-Stable Palladium(I) Dimer |
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Authors: | Indrek Kalvet Kristina Deckers Dr. Ignacio Funes-Ardoiz Guillaume Magnin Theresa Sperger Marius Kremer Prof. Dr. Franziska Schoenebeck |
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Affiliation: | Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany |
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Abstract: | 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 PdI dimer and enables straightforward access to diversely substituted therapeutically important adamantylarenes in 5–30 min. |
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Keywords: | Chemoselectivität Kreuzkupplung DFT-Berechnungen Homogene Katalyse Palladium |
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