Top Organomet Chem (2021) 69: 153–206
https://doi.org/10.1007/3418_2020_64
# The Author(s), under exclusive license to Springer Nature Switzerland AG 2020
Published online: 11 December 2020
Iridium-Catalyzed Asymmetric
Hydrogenation
Jèssica Margalef, Oscar Pàmies, and Montserrat Diéguez
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
2 Ir-Catalyzed Asymmetric Hydrogenation of Unfunctionalized Olefins or with Poorly
Coordinative Groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
2.1 Di- and Trisubstituted Unfunctionalized Olefins or with Poorly Coordinative
Groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
2.2 Tetrasubstituted Unfunctionalized Olefins or with Poorly Coordinative Groups . . . 171
3 Ir-Catalyzed Asymmetric Hydrogenation of Olefins Containing Coordinating Groups . . . 173
3.1 Ir-Catalyzed Asymmetric Hydrogenation of Carboxylic Acids . . . . . . . . . . . . . . . . . . . . . . 174
3.2 Ir-Catalyzed Asymmetric Hydrogenation of Nitroolefins . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
3.3 Ir-Catalyzed Asymmetric Hydrogenation of Enamines, Enamides, and Allylic
Amines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
4 Asymmetric Ir-Catalyzed Hydrogenation of Imines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
4.1 Asymmetric Hydrogenation Using Cationic Catalyst Precursors . . . . . . . . . . . . . . . . . . . . 184
4.2 Asymmetric Hydrogenation Using Neutral Catalyst Precursors . . . . . . . . . . . . . . . . . . . . . 185
5 Ir-Catalyzed Asymmetric Hydrogenation of Ketones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 192
5.1 P-Donor-Based Ligands . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 192
5.2 Non-P-Donor-Based Ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
6 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
Abstract In this chapter, we describe the development in homogeneous
Ir-catalyzed asymmetric hydrogenation with particular emphasis on the achievements made during the last 10 years. We also present their application to the
synthesis of complex molecules. The first section deals with the hydrogenation of
unfunctionalized olefins or with poorly coordinative groups. The second section
includes the advances made in the hydrogenation of functionalized olefins. The last
two sections cover the hydrogenation of imines and ketones, respectively.
J. Margalef, O. Pàmies, and M. Diéguez (*)
Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, Tarragona, Spain
e-mail: montserrat.dieguez@urv.cat