Ligand-Controlled α- and β-Arylation of Acyclic N-Boc Amines

The palladium‐catalyzed ligand‐controlled arylation of α‐zincated acyclic amines, obtained by directed α‐lithiation and transmetalation, is described. Whereas PtBu3 gave rise to α‐arylated Boc‐protected amines, more flexible N‐phenylazole‐based phosphine ligands induced major β‐arylation through mig...

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Published inAngewandte Chemie International Edition Vol. 53; no. 10; pp. 2678 - 2682
Main Authors Millet, Anthony, Dailler, David, Larini, Paolo, Baudoin, Olivier
Format Journal Article
LanguageEnglish
Published Weinheim WILEY-VCH Verlag 03.03.2014
WILEY‐VCH Verlag
Wiley
Subjects
Amines - chemical synthesis
Amines - chemistry
arylation
Catalysis
Chemistry
Chemistry, Multidisciplinary
cross-coupling
CC coupling
density functional calculations
Ligands
Molecular Conformation
palladium
Palladium - chemistry
Physical Sciences
Science & Technology
CC coupling
density functional calculations
SUZUKI
CARBON
SCOPE
IN-SITU IR
cross-coupling
SECONDARY
palladium
ARYL
LITHIATION
arylation
CC coupling
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Summary:The palladium‐catalyzed ligand‐controlled arylation of α‐zincated acyclic amines, obtained by directed α‐lithiation and transmetalation, is described. Whereas PtBu3 gave rise to α‐arylated Boc‐protected amines, more flexible N‐phenylazole‐based phosphine ligands induced major β‐arylation through migrative cross‐coupling. All manner of control: The arylation of α‐zincated acyclic Boc‐protected amines was selectively performed at the α‐ or β‐position in a ligand‐controlled manner. α‐Arylation occurs by direct reductive elimination of the α‐palladated intermediate whereas β‐arylation involves palladium migration along the alkyl chain. Boc=tert‐butoxycarbonyl.
Bibliography:istex:6991B02719A4100A2D718AC01625A37089AECEE1
Institut Universitaire de France
Computational work performed by Dr. P. Larini. We thank the Agence Nationale de la Recherche (programme blanc "EnolFun") and Institut Universitaire de France for financial support of this work. We also thank Prof. B. Andrioletti and L. Sandjong-Kuigwa for free access to and assistance with in situ IR instrument and Dr. E. Clot for fruitful discussions and comments.
Agence Nationale de la Recherche
ArticleID:ANIE201310904
ark:/67375/WNG-HPP32WVQ-4
Computational work performed by Dr. P. Larini. We thank the Agence Nationale de la Recherche (programme blanc “EnolFun”) and Institut Universitaire de France for financial support of this work. We also thank Prof. B. Andrioletti and L. Sandjong‐Kuigwa for free access to and assistance with in situ IR instrument and Dr. E. Clot for fruitful discussions and comments.
ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
content type line 23
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201310904