Top Organomet Chem (2016) 56: 1–18
DOI: 10.1007/3418_2015_129
# Springer International Publishing Switzerland 2015
Published online: 8 August 2015
Iron-Catalyzed C–H Bond Activation
Laurean Ilies and Eiichi Nakamura
Abstract Iron-catalyzed C–H bond activation followed by C–C bond formation
has received much attention in recent years, motivated by the environmental and
economical merits of iron, as well as the scientific challenge in controlling and
understanding the reactivity of iron species. This review describes the utilization of
iron as a catalyst for directed C–H bond activation, followed by C–C bond formation. Catalytic activation of C(sp
2 )-H and C(sp
3 -H) bonds, followed by oxidative
reaction with nucleophiles, or reaction with electrophiles is described. Reactions of
substrates possessing a directing group are mainly discussed, but other substrates
are also presented. Carbon–heteroatom bond formation is also briefly discussed.
Keywords C–C bond formation Á C–H bond activation Á Iron
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2 Functionalization of C(sp
2
)–H Bonds . . . . . . . . . . . . .. . . . . . . . . . . . . .. . . . . . . . . . . . .. . . . . . . . . . . . .. . . 2
2.1 Substrates Possessing a Directing Group . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.2 Other Substrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3 Functionalization of C(sp
3
)–H Bonds . . . . . . . . . . . . .. . . . . . . . . . . . . .. . . . . . . . . . . . .. . . . . . . . . . . . .. . . 14
3.1 Substrates Possessing a Directing Group . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
3.2 Other Substrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
4 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
L. Ilies (*) and E. Nakamura (*)
Department of Chemistry, The University of Tokyo, School of Science, Hongo, Bunkyo-ku,
Tokyo 113-0033, Japan
e-mail: laur@chem.s.u-tokyo.ac.jp; nakamura@chem.s.u-tokyo.ac.jp
DOI: 10.1007/3418_2015_129
# Springer International Publishing Switzerland 2015
Published online: 8 August 2015
Iron-Catalyzed C–H Bond Activation
Laurean Ilies and Eiichi Nakamura
Abstract Iron-catalyzed C–H bond activation followed by C–C bond formation
has received much attention in recent years, motivated by the environmental and
economical merits of iron, as well as the scientific challenge in controlling and
understanding the reactivity of iron species. This review describes the utilization of
iron as a catalyst for directed C–H bond activation, followed by C–C bond formation. Catalytic activation of C(sp
2 )-H and C(sp
3 -H) bonds, followed by oxidative
reaction with nucleophiles, or reaction with electrophiles is described. Reactions of
substrates possessing a directing group are mainly discussed, but other substrates
are also presented. Carbon–heteroatom bond formation is also briefly discussed.
Keywords C–C bond formation Á C–H bond activation Á Iron
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2 Functionalization of C(sp
2
)–H Bonds . . . . . . . . . . . . .. . . . . . . . . . . . . .. . . . . . . . . . . . .. . . . . . . . . . . . .. . . 2
2.1 Substrates Possessing a Directing Group . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.2 Other Substrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3 Functionalization of C(sp
3
)–H Bonds . . . . . . . . . . . . .. . . . . . . . . . . . . .. . . . . . . . . . . . .. . . . . . . . . . . . .. . . 14
3.1 Substrates Possessing a Directing Group . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
3.2 Other Substrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
4 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
L. Ilies (*) and E. Nakamura (*)
Department of Chemistry, The University of Tokyo, School of Science, Hongo, Bunkyo-ku,
Tokyo 113-0033, Japan
e-mail: laur@chem.s.u-tokyo.ac.jp; nakamura@chem.s.u-tokyo.ac.jp