Top Organomet Chem (2013) 46: 55–86
DOI: 10.1007/3418_2012_57
# Springer-Verlag Berlin Heidelberg 2012
Published online: 13 February 2013
Metal-Catalyzed C(sp
2
)–N Bond Formation
Arkaitz Correa and Carsten Bolm
Abstract During the last decades a powerful set of protocols featuring C(sp
2
)–N
bond formation have emerged as convenient alternatives for the assembly of enamine
and enamides. Those methods consist of mostly palladium-catalyzed oxidative
amidations of alkenes and both palladium- and copper-catalyzed cross-couplings
between generally vinyl halides or pseudohalides and amines or amides. In this
review recent advances in both types of processes will be disclosed. Additionally,
the synthetic value of the title processes will be illustrated by describing relevant total
syntheses of natural products involving vinylation process as the key step.
Keywords Copper Á Cross-coupling Á Enamide Á Enamine Á Metal catalysis Á
Palladium Á Vinylation
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
2 Oxidative Amination/Amidation of Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
3 Cross-Coupling Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
3.1 Palladium-Catalyzed Cross-Couplings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
3.2 Copper-Catalyzed Cross-Couplings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
4 Conclusion and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
A. Correa and C. Bolm (*)
Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1,
52056 Aachen, Germany
e-mail: carsten.bolm@oc.rwth-aachen.de
DOI: 10.1007/3418_2012_57
# Springer-Verlag Berlin Heidelberg 2012
Published online: 13 February 2013
Metal-Catalyzed C(sp
2
)–N Bond Formation
Arkaitz Correa and Carsten Bolm
Abstract During the last decades a powerful set of protocols featuring C(sp
2
)–N
bond formation have emerged as convenient alternatives for the assembly of enamine
and enamides. Those methods consist of mostly palladium-catalyzed oxidative
amidations of alkenes and both palladium- and copper-catalyzed cross-couplings
between generally vinyl halides or pseudohalides and amines or amides. In this
review recent advances in both types of processes will be disclosed. Additionally,
the synthetic value of the title processes will be illustrated by describing relevant total
syntheses of natural products involving vinylation process as the key step.
Keywords Copper Á Cross-coupling Á Enamide Á Enamine Á Metal catalysis Á
Palladium Á Vinylation
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
2 Oxidative Amination/Amidation of Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
3 Cross-Coupling Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
3.1 Palladium-Catalyzed Cross-Couplings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
3.2 Copper-Catalyzed Cross-Couplings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
4 Conclusion and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
A. Correa and C. Bolm (*)
Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1,
52056 Aachen, Germany
e-mail: carsten.bolm@oc.rwth-aachen.de