Top Organomet Chem (2013) 46: 173–204
DOI: 10.1007/3418_2013_69
# Springer-Verlag Berlin Heidelberg 2013
Published online: 1 October 2013
Copper-Catalyzed C(aryl)–N Bond
Formation
Florian Monnier and Marc Taillefer
Abstract Although requiring the use of stoichiometric amounts of metal and
harsh conditions, the copper-mediated coupling reactions of aryl halides with amines
and phenols (Ullmann condensations), amides and carbamates (Ullmann–Goldberg
condensations), or activated methylene compounds (Ullmann–Hurtley condensations)
have been for a long time useful methods for the formation of C(aryl)–N, C(aryl)–O,
and C(aryl)–C bonds. In 2001, a renaissance of the Ullmann reaction has been initiated
with the discovery of versatile new copper catalytic systems for C–C, C–N, or C–O
coupling under mild temperature conditions.
This chapter covers more specifically the copper-catalyzed C(aryl)–N bond
formation via the coupling of aryl halides with nitrogen nucleophiles such as
N-heterocycles, amines, anilines, amides, ammonia, azides, hydroxylamines, nitrite
salts or phosphonic amides. The C(aryl)–N bond formation as a result of the
coupling between these nucleophiles and arylboronic acids (the Chan–Lam
reaction) will be also presented. It is worth noting that this chapter mainly focuses
on the most significant results and important breakthroughs in this field.
Keywords Copper Á Arylation Á N-nucleophiles Á Catalysis
Contents
1 Introduction and Scope of the Chapter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
2 C–N Bond Formation from Aryl Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
2.1 Coupling Reactions of Aryl Halides with N-Heterocycles and Cyclic Amides . . . . 175
2.2 Coupling Reactions of Aryl Halides with Alkyl and Aryl Amines and with
Noncyclic Amides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
2.3 Coupling Reactions of Aryl Halides with NH 3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 184
2.4 Miscellaneous Coupling Reactions of Aryl Halides with N-Nucleophiles . . . . . . . . . 188
F. Monnier and M. Taillefer (*)
Institut Charles Gerhardt Montpellier, AM2N, ENSCM, 8, rue de l’Ecole Normale,
34296 Montpellier, France
e-mail: florian.monnier@enscm.fr; marc.taillefer@enscm.fr
DOI: 10.1007/3418_2013_69
# Springer-Verlag Berlin Heidelberg 2013
Published online: 1 October 2013
Copper-Catalyzed C(aryl)–N Bond
Formation
Florian Monnier and Marc Taillefer
Abstract Although requiring the use of stoichiometric amounts of metal and
harsh conditions, the copper-mediated coupling reactions of aryl halides with amines
and phenols (Ullmann condensations), amides and carbamates (Ullmann–Goldberg
condensations), or activated methylene compounds (Ullmann–Hurtley condensations)
have been for a long time useful methods for the formation of C(aryl)–N, C(aryl)–O,
and C(aryl)–C bonds. In 2001, a renaissance of the Ullmann reaction has been initiated
with the discovery of versatile new copper catalytic systems for C–C, C–N, or C–O
coupling under mild temperature conditions.
This chapter covers more specifically the copper-catalyzed C(aryl)–N bond
formation via the coupling of aryl halides with nitrogen nucleophiles such as
N-heterocycles, amines, anilines, amides, ammonia, azides, hydroxylamines, nitrite
salts or phosphonic amides. The C(aryl)–N bond formation as a result of the
coupling between these nucleophiles and arylboronic acids (the Chan–Lam
reaction) will be also presented. It is worth noting that this chapter mainly focuses
on the most significant results and important breakthroughs in this field.
Keywords Copper Á Arylation Á N-nucleophiles Á Catalysis
Contents
1 Introduction and Scope of the Chapter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
2 C–N Bond Formation from Aryl Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
2.1 Coupling Reactions of Aryl Halides with N-Heterocycles and Cyclic Amides . . . . 175
2.2 Coupling Reactions of Aryl Halides with Alkyl and Aryl Amines and with
Noncyclic Amides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
2.3 Coupling Reactions of Aryl Halides with NH 3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 184
2.4 Miscellaneous Coupling Reactions of Aryl Halides with N-Nucleophiles . . . . . . . . . 188
F. Monnier and M. Taillefer (*)
Institut Charles Gerhardt Montpellier, AM2N, ENSCM, 8, rue de l’Ecole Normale,
34296 Montpellier, France
e-mail: florian.monnier@enscm.fr; marc.taillefer@enscm.fr