Top Organomet Chem (2021) 68: 227–262
https://doi.org/10.1007/3418_2020_66
# Springer Nature Switzerland AG 2020
Published online: 30 October 2020
The Role of Metal-Ligand Cooperation
in Manganese(I)-Catalyzed Hydrogenation/
Dehydrogenation Reactions
Stefan Weber and Karl Kirchner
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
2 Hydrogenation Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
2.1 Hydrogenation of Aldehydes and Ketones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230
2.2 Hydrogenation of Esters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
2.3 Hydrogenation of Amides, Imines, Nitriles, and Heterocycles . . . . . . . . . . . . . . . . . . . . . . 235
2.4 Reduction of Carbon Dioxide, Carbonates, and Carbamates . . . . . . . . . . . . . . . . . . . . . . . . 239
2.5 Hydrogenation of Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
3 Dehydrogenation and Coupling Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . 243
3.1 Acceptorless Dehydrogenative Coupling (ADC) Reactions . . . . . . . . . . . . . . . . . . . . . . . . . 243
3.2 Synthesis of Aldimines, Cyclic Imides, and Amides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
3.3 Synthesis of Esters and Functionalization of Nitriles and Alkanes . . . . . . . . . . . . . . . . . . 246
3.4 Synthesis and Derivatization of Heterocycles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 248
3.5 Hydrogen-Borrowing Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249
3.6 Alkylation of Amines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
3.7 Alkylation of Alcohols and Ketones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
3.8 Alkylation of Nitriles and Sulfonamide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
3.9 Upgrading of Ethanol into 1-Butanol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
4 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 258
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 259
Abstract The usage of earth-abundant metals as catalysts for chemical synthesis in
order to install more sustainable reactions is a major goal in modern synthesis.
Within the last few years, well-defined manganese complexes appeared in academic
research and were proven to be a powerful player in the field of benign oxidation and
reduction reactions. Hydrogenation of polarized double bonds such as aldehydes,
ketones, esters, amides, and nitriles, but also carbon-carbon double bonds, can
efficiently be achieved by well-defined manganese complexes. In the case of
S. Weber and K. Kirchner (*)
Institute of Applied Synthetic Chemistry, Vienna University of Technology, Vienna, Austria
e-mail: karl.kirchner@tuwien.ac.at
https://doi.org/10.1007/3418_2020_66
# Springer Nature Switzerland AG 2020
Published online: 30 October 2020
The Role of Metal-Ligand Cooperation
in Manganese(I)-Catalyzed Hydrogenation/
Dehydrogenation Reactions
Stefan Weber and Karl Kirchner
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
2 Hydrogenation Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
2.1 Hydrogenation of Aldehydes and Ketones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230
2.2 Hydrogenation of Esters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
2.3 Hydrogenation of Amides, Imines, Nitriles, and Heterocycles . . . . . . . . . . . . . . . . . . . . . . 235
2.4 Reduction of Carbon Dioxide, Carbonates, and Carbamates . . . . . . . . . . . . . . . . . . . . . . . . 239
2.5 Hydrogenation of Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
3 Dehydrogenation and Coupling Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . 243
3.1 Acceptorless Dehydrogenative Coupling (ADC) Reactions . . . . . . . . . . . . . . . . . . . . . . . . . 243
3.2 Synthesis of Aldimines, Cyclic Imides, and Amides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
3.3 Synthesis of Esters and Functionalization of Nitriles and Alkanes . . . . . . . . . . . . . . . . . . 246
3.4 Synthesis and Derivatization of Heterocycles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 248
3.5 Hydrogen-Borrowing Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249
3.6 Alkylation of Amines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
3.7 Alkylation of Alcohols and Ketones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
3.8 Alkylation of Nitriles and Sulfonamide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
3.9 Upgrading of Ethanol into 1-Butanol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
4 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 258
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 259
Abstract The usage of earth-abundant metals as catalysts for chemical synthesis in
order to install more sustainable reactions is a major goal in modern synthesis.
Within the last few years, well-defined manganese complexes appeared in academic
research and were proven to be a powerful player in the field of benign oxidation and
reduction reactions. Hydrogenation of polarized double bonds such as aldehydes,
ketones, esters, amides, and nitriles, but also carbon-carbon double bonds, can
efficiently be achieved by well-defined manganese complexes. In the case of
S. Weber and K. Kirchner (*)
Institute of Applied Synthetic Chemistry, Vienna University of Technology, Vienna, Austria
e-mail: karl.kirchner@tuwien.ac.at