Directed C-H Bond Oxidation of Bridged Cycloalkanes Catalyzed by Palladium(II) Acetate

Marta Larrosa; Benjamin Zonker; Jannis Volkmann; Felix Wech; Christian Logemann; Heike Hausmann; Radim Hrdina

doi:10.1002/chem.201800550

Directed C-H Bond Oxidation of Bridged Cycloalkanes Catalyzed by Palladium(II) Acetate

Chemistry. 2018 Apr 20;24(23):6269-6276. doi: 10.1002/chem.201800550. Epub 2018 Mar 22.

Authors

Marta Larrosa¹, Benjamin Zonker¹, Jannis Volkmann¹, Felix Wech¹, Christian Logemann², Heike Hausmann¹, Radim Hrdina¹

Affiliations

¹ Institute of Organic Chemistry, Justus-Liebig University, Heinrich-Buff-Ring 17, 35392, Giessen, Germany.
² Institute of Inorganic and Analytical Chemistry, Justus-Liebig University, Heinrich-Buff-Ring 17, 35392, Giessen, Germany.

PMID: 29488690
DOI: 10.1002/chem.201800550

Abstract

We have developed a synthesis of 1,2-substituted adamantane carboxylic acids and further bridged cycloalkanes (cage compounds) by palladium acetate-catalyzed C-H bond oxidation. Acetoxylation of cycloalkane framework was performed using picolylamide as a directing group. Modification of the substrate, ligand design and variation of reaction conditions enabled us to study the mechanism of acetoxylation of aliphatic compounds. Post-functionalization reactions and cleavage of the directing group were developed. For the first time the synthesis and characterization of a β-C₃ -tri-substituted adamantane derivatives was achieved.

Keywords: C−H activation; acetoxylation; adamantane; cage compounds; palladium.