Top Organomet Chem (2021) 69: 1–66
https://doi.org/10.1007/3418_2020_56
# The Author(s), under exclusive license to Springer Nature Switzerland AG 2020,
corrected publication 2020
Published online: 4 August 2020
Iridium-Catalyzed Dehydrogenative
Reactions
Takuya Shimbayashi and Ken-ichi Fujita
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2 Dehydrogenation of Alkanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3 Dehydrogenation of Heterocyclic Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.1 Dehydrogenation of N-Heterocyclic Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.2 Dehydrogenation of Other Heterocyclic Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
3.3 N-Heteroarene Synthesis via Combination of Ring Construction–Dehydrogenation . . . 20
4 Dehydrogenation of Alcohols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
4.1 Dehydrogenative Oxidation of Alcohols to Aldehydes and Ketones . . . . . . . . . . . . . . . . . 27
4.2 Dehydrogenative Oxidation of Primary Alcohols to Esters, Carboxylic Acids,
and Acetals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
4.3 Dehydrogenative Decarbonylation of Primary Alcohols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
4.4 Dehydrogenative Cross-Coupling Reactions Involving Alcohols . . . . . . . . . . . . . . . . . . . . 36
4.5 Synthesis of N-Heterocycles Based on Alcohol Dehydrogenation . . . . . . . . . . . . . . . . . . . 38
4.6 Other Reactions Based on Alcohol Dehydrogenation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
5 Dehydrogenation of Formic Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
6 Dehydrogenative Borylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
6.1 Aryl and Alkyl Group Borylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
6.2 Terminal Alkyne Borylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
7 Miscellaneous . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
8 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
Abstract This chapter summarizes the recent advances in homogeneous iridium
complex-catalyzed dehydrogenative reactions, covering the dehydrogenation of
alkanes, heterocyclic compounds, alcohols, and formic acid. Both simple reactions
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
T. Shimbayashi and K. Fujita (*)
Graduate School of Human and Environmental Studies, Kyoto University, Kyoto, Japan
e-mail: shimbayashi.takuya.5z@kyoto-u.ac.jp; fujita.kenichi.6a@kyoto-u.ac.jp
https://doi.org/10.1007/3418_2020_56
# The Author(s), under exclusive license to Springer Nature Switzerland AG 2020,
corrected publication 2020
Published online: 4 August 2020
Iridium-Catalyzed Dehydrogenative
Reactions
Takuya Shimbayashi and Ken-ichi Fujita
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2 Dehydrogenation of Alkanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3 Dehydrogenation of Heterocyclic Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.1 Dehydrogenation of N-Heterocyclic Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.2 Dehydrogenation of Other Heterocyclic Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
3.3 N-Heteroarene Synthesis via Combination of Ring Construction–Dehydrogenation . . . 20
4 Dehydrogenation of Alcohols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
4.1 Dehydrogenative Oxidation of Alcohols to Aldehydes and Ketones . . . . . . . . . . . . . . . . . 27
4.2 Dehydrogenative Oxidation of Primary Alcohols to Esters, Carboxylic Acids,
and Acetals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
4.3 Dehydrogenative Decarbonylation of Primary Alcohols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
4.4 Dehydrogenative Cross-Coupling Reactions Involving Alcohols . . . . . . . . . . . . . . . . . . . . 36
4.5 Synthesis of N-Heterocycles Based on Alcohol Dehydrogenation . . . . . . . . . . . . . . . . . . . 38
4.6 Other Reactions Based on Alcohol Dehydrogenation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
5 Dehydrogenation of Formic Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
6 Dehydrogenative Borylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
6.1 Aryl and Alkyl Group Borylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
6.2 Terminal Alkyne Borylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
7 Miscellaneous . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
8 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
Abstract This chapter summarizes the recent advances in homogeneous iridium
complex-catalyzed dehydrogenative reactions, covering the dehydrogenation of
alkanes, heterocyclic compounds, alcohols, and formic acid. Both simple reactions
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
T. Shimbayashi and K. Fujita (*)
Graduate School of Human and Environmental Studies, Kyoto University, Kyoto, Japan
e-mail: shimbayashi.takuya.5z@kyoto-u.ac.jp; fujita.kenichi.6a@kyoto-u.ac.jp