Top Organomet Chem (2013) 46: 1–54
DOI: 10.1007/3418_2012_56
# Springer-Verlag Berlin Heidelberg 2012
Published online: 13 February 2013
Palladium-Catalyzed sp
2 C–N Bond Forming
Reactions: Recent Developments
and Applications
Georgia S. Lemen and John P. Wolfe
Abstract This review describes recent developments in the field of Pd-catalyzed sp
2
C–N bond formation that were reported in the primary literature between 2004 and
2008. These transformations have found widespread application in both academia
and industry. A brief history of the field is presented, followed by recent improvements
and extensions of the methodology. Applications of these transformations to the
synthesis of useful compounds, including biologically active molecules, and materials,
are described.
Keywords Arylamines Á Cross-coupling Á Heterocycles Á Materials Á N-Arylation Á
Natural products
Contents
1 Introduction and Scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2 Early Work Prior to 2004 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3 Improvements and Extensions of Pd-Catalyzed N-Arylation Methods . . . . . . . . . . . . . . . . . . . . 6
3.1 New Ligands and Continued Exploration
of Existing Ligands . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . .. . . . . . . . 6
3.2 Modified Reaction Conditions or Techniques That Facilitate Pd-Catalyzed
N-Arylations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.3 New Nucleophiles and Electrophiles or Improved Reactions of Previously
Studied Nucleophiles and Electrophiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
4 Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
4.1 Synthesis of Heterocycles via Reaction Sequences Involving N-Arylation . . . . . . . . . . 24
4.2 Synthesis of Natural Products and Pharmaceutical Target Molecules . . . . . . . . . . . . . . . 27
4.3 Synthesis of Molecules with Potential Materials Chemistry Applications . . . . . . . . . . . 30
4.4 Use of N-Arylation Reactions for the Synthesis of Ligands for Metal Complexes and
Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
4.5 Process Scale Applications of Pd-Catalyzed N-Arylation Reactions . . . . . . . . . . . . . . . . . 40
5 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
G.S. Lemen and J.P. Wolfe (*)
Department of Chemistry, University of Michigan, Ann Arbor, MI 48109-1055, USA
e-mail: jpwolfe@umich.edu
DOI: 10.1007/3418_2012_56
# Springer-Verlag Berlin Heidelberg 2012
Published online: 13 February 2013
Palladium-Catalyzed sp
2 C–N Bond Forming
Reactions: Recent Developments
and Applications
Georgia S. Lemen and John P. Wolfe
Abstract This review describes recent developments in the field of Pd-catalyzed sp
2
C–N bond formation that were reported in the primary literature between 2004 and
2008. These transformations have found widespread application in both academia
and industry. A brief history of the field is presented, followed by recent improvements
and extensions of the methodology. Applications of these transformations to the
synthesis of useful compounds, including biologically active molecules, and materials,
are described.
Keywords Arylamines Á Cross-coupling Á Heterocycles Á Materials Á N-Arylation Á
Natural products
Contents
1 Introduction and Scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2 Early Work Prior to 2004 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3 Improvements and Extensions of Pd-Catalyzed N-Arylation Methods . . . . . . . . . . . . . . . . . . . . 6
3.1 New Ligands and Continued Exploration
of Existing Ligands . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . .. . . . . . . . 6
3.2 Modified Reaction Conditions or Techniques That Facilitate Pd-Catalyzed
N-Arylations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.3 New Nucleophiles and Electrophiles or Improved Reactions of Previously
Studied Nucleophiles and Electrophiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
4 Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
4.1 Synthesis of Heterocycles via Reaction Sequences Involving N-Arylation . . . . . . . . . . 24
4.2 Synthesis of Natural Products and Pharmaceutical Target Molecules . . . . . . . . . . . . . . . 27
4.3 Synthesis of Molecules with Potential Materials Chemistry Applications . . . . . . . . . . . 30
4.4 Use of N-Arylation Reactions for the Synthesis of Ligands for Metal Complexes and
Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
4.5 Process Scale Applications of Pd-Catalyzed N-Arylation Reactions . . . . . . . . . . . . . . . . . 40
5 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
G.S. Lemen and J.P. Wolfe (*)
Department of Chemistry, University of Michigan, Ann Arbor, MI 48109-1055, USA
e-mail: jpwolfe@umich.edu