Ligand-controlled β-selective C(sp3)–H arylation of N-Boc-piperidines

We report a general palladium-catalyzed β-arylation of Boc-piperidines, which yields a variety of valuable 3-arylpiperidines in a simple and direct manner. The β- vs. α-arylation selectivity was controlled by the ligand, with flexible biarylphosphines providing mainly the desired β-arylated products...

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Bibliographic Details
Published inChemical science (Cambridge) Vol. 4; no. 5; pp. 2241 - 2247
Main Authors Millet, Anthony, Larini, Paolo, Clot, Eric, Baudoin, Olivier
Format Journal Article
LanguageEnglish
Published The Royal Society of Chemistry 01.01.2013
Subjects
Catalysis
Chemical Sciences
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Summary:We report a general palladium-catalyzed β-arylation of Boc-piperidines, which yields a variety of valuable 3-arylpiperidines in a simple and direct manner. The β- vs. α-arylation selectivity was controlled by the ligand, with flexible biarylphosphines providing mainly the desired β-arylated products whereas more rigid biarylphosphines mainly furnished the more classical α-arylated products. The computed reaction mechanism (DFT), studied from the common α-palladated intermediate, indicated that the reductive elimination steps leading to the α- and β-arylated products are selectivity-determining. Moreover, the experimental trend obtained with different ligands was well reproduced by the calculations.
ISSN:2041-6520
2041-6539
DOI:10.1039/c3sc50428j