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...

Full description

Saved in:
Bibliographic Details
Published in:Chemical science (Cambridge) 2013-01, Vol.4 (5), p.2241-2247
Main Authors: Millet, Anthony, Larini, Paolo, Clot, Eric, Baudoin, Olivier
Format: Article
Language:English
Subjects:
Catalysis
Chemical Sciences
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
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