Top Organomet Chem (2021) 69: 227–270
https://doi.org/10.1007/3418_2020_55
# The Author(s), under exclusive license to Springer Nature Switzerland AG 2020,
corrected publication 2020
Published online: 8 August 2020
Iridium-Catalyzed Silylation
Manuel Iglesias and Luis A. Oro
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
2 Hydrosilylation Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
2.1 Hydrosilylation of Ketones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
2.2 Hydrosilylation of Imines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
2.3 Hydrosilylation of Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
2.4 Hydrosilylation of Alkynes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244
2.5 Hydrosilylation of Cyclopropanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249
3 Silylation of C–H Bonds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
3.1 Silylation of Alkynes and Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
3.2 Silylation of Arenes and Heteroarenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
3.3 Silylation of Alkanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261
4 Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 266
Abstract In this chapter, homogeneous iridium-catalyzed silylation reactions are
reviewed, focusing primarily on their synthetic utility. Additionally, relevant catalytic cycles are commented, paying especial attention to those that are more representative of each type of process. The chapter is divided into two main types of
reactions, namely, hydrosilylation and C–H bond silylation. The former deals with
the hydrosilylation of polar unsaturated bonds (ketones and imines) and non-polar
unsaturated bonds (alkenes and alkynes). The latter covers the directed and
non-directed C–H bond silylation of alkenes, alkynes, arenes, and alkanes – mainly
comprising dehydrogenative silylation reactions, which may occur in the presence or
absence of a hydrogen acceptor.
The original version of this chapter was revised. A correction to this chapter can be found at
https://doi.org/10.1007/3418_2020_73
M. Iglesias (*) and L. A. Oro (*)
Department of Inorganic Chemistry, ISQCH, University of Zaragoza-CSIC, Zaragoza, Spain
e-mail: miglesia@unizar.es; oro@unizar.es
https://doi.org/10.1007/3418_2020_55
# The Author(s), under exclusive license to Springer Nature Switzerland AG 2020,
corrected publication 2020
Published online: 8 August 2020
Iridium-Catalyzed Silylation
Manuel Iglesias and Luis A. Oro
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
2 Hydrosilylation Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
2.1 Hydrosilylation of Ketones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
2.2 Hydrosilylation of Imines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
2.3 Hydrosilylation of Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
2.4 Hydrosilylation of Alkynes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244
2.5 Hydrosilylation of Cyclopropanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249
3 Silylation of C–H Bonds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
3.1 Silylation of Alkynes and Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
3.2 Silylation of Arenes and Heteroarenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
3.3 Silylation of Alkanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261
4 Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 266
Abstract In this chapter, homogeneous iridium-catalyzed silylation reactions are
reviewed, focusing primarily on their synthetic utility. Additionally, relevant catalytic cycles are commented, paying especial attention to those that are more representative of each type of process. The chapter is divided into two main types of
reactions, namely, hydrosilylation and C–H bond silylation. The former deals with
the hydrosilylation of polar unsaturated bonds (ketones and imines) and non-polar
unsaturated bonds (alkenes and alkynes). The latter covers the directed and
non-directed C–H bond silylation of alkenes, alkynes, arenes, and alkanes – mainly
comprising dehydrogenative silylation reactions, which may occur in the presence or
absence of a hydrogen acceptor.
The original version of this chapter was revised. A correction to this chapter can be found at
https://doi.org/10.1007/3418_2020_73
M. Iglesias (*) and L. A. Oro (*)
Department of Inorganic Chemistry, ISQCH, University of Zaragoza-CSIC, Zaragoza, Spain
e-mail: miglesia@unizar.es; oro@unizar.es