Top Organomet Chem (2021) 69: 207–226
https://doi.org/10.1007/3418_2020_53
# The Author(s), under exclusive license to Springer Nature Switzerland AG 2020,
corrected publication 2020
Published online: 30 July 2020
Iridium-Catalyzed Undirected
Homogeneous C–H Borylation Reaction
Elena Fernández
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 208
2 C–H Borylation of Heteroarenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
3 C–H Borylation of Arenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 214
4 C–H Borylation of Alkanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 224
Abstract The present chapter describes the intense efforts devoted to develop new
concepts from 2014 up today in the iridium-catalyzed undirected homogeneous C–H
borylation of heteroarenes, arenes, and alkanes. Selectivity issues are principally
highlighted in this chapter since no directed groups are included in these approaches,
but improved ligands are responsible of the new trends instead. In parallel, mechanistic insights on the C–B bond formation analyzed through density functional
theory orientate the suggestion of alternative catalytic cycles, to understand the
high level of selectivity on Csp
2 -H and Csp
3 -H borylation. This area of work
keeps very active because of the inherent interest on the C–B bond formation
allowing access to multifunctionalized products, in a straightforward manner.
Keywords Alkanes · Arenes · Bis(pinacolato)diboron · Catalytic cycle · C–H
borylation · Heteroarenes · Iridium · Phenanthroline · Pinacolborane · Selectivity
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
E. Fernández (*)
Dept. Química Física i Inorgànica, Faculty of Chemistry, Tarragona, Spain
e-mail: mariaelena.fernandez@urv.cat
https://doi.org/10.1007/3418_2020_53
# The Author(s), under exclusive license to Springer Nature Switzerland AG 2020,
corrected publication 2020
Published online: 30 July 2020
Iridium-Catalyzed Undirected
Homogeneous C–H Borylation Reaction
Elena Fernández
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 208
2 C–H Borylation of Heteroarenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
3 C–H Borylation of Arenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 214
4 C–H Borylation of Alkanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 224
Abstract The present chapter describes the intense efforts devoted to develop new
concepts from 2014 up today in the iridium-catalyzed undirected homogeneous C–H
borylation of heteroarenes, arenes, and alkanes. Selectivity issues are principally
highlighted in this chapter since no directed groups are included in these approaches,
but improved ligands are responsible of the new trends instead. In parallel, mechanistic insights on the C–B bond formation analyzed through density functional
theory orientate the suggestion of alternative catalytic cycles, to understand the
high level of selectivity on Csp
2 -H and Csp
3 -H borylation. This area of work
keeps very active because of the inherent interest on the C–B bond formation
allowing access to multifunctionalized products, in a straightforward manner.
Keywords Alkanes · Arenes · Bis(pinacolato)diboron · Catalytic cycle · C–H
borylation · Heteroarenes · Iridium · Phenanthroline · Pinacolborane · Selectivity
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
E. Fernández (*)
Dept. Química Física i Inorgànica, Faculty of Chemistry, Tarragona, Spain
e-mail: mariaelena.fernandez@urv.cat