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Selective ortho-Functionalization of Adamantylarenes Enabled by Dispersion and an Air-Stable Palladium(I) Dimer.

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 Pd^I dimer and enables straightforward access to diversely substituted therapeutically important adamantylarenes in 5-30 min.

SUBMITTER: Kalvet I

PROVIDER: S-EPMC7317867 | biostudies-literature | 2020 May

REPOSITORIES: biostudies-literature

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Selective ortho-Functionalization of Adamantylarenes Enabled by Dispersion and an Air-Stable Palladium(I) Dimer.

Kalvet Indrek I Deckers Kristina K Funes-Ardoiz Ignacio I Magnin Guillaume G Sperger Theresa T Kremer Marius M Schoenebeck Franziska F

Angewandte Chemie (International ed. in English) 20200317 20

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- ...[more]

PMID: 32065717

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