Top Organomet Chem (2021) 69: 271–302
https://doi.org/10.1007/3418_2020_58
# The Author(s), under exclusive license to Springer Nature Switzerland AG 2020,
corrected publication 2020
Published online: 8 August 2020
Iridium Catalysts for Hydrogen Isotope
Exchange
Marc Reid
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 272
1.1 Isotopes and Isotopic Labeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 272
1.2 Applications of Hydrogen Isotope Exchange . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 273
1.3 Synthetic Methods in HIE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 273
2 Ortho-Directed Iridium-Catalyzed HIE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 274
2.1 Early Developments in Ortho-Directed HIE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 275
2.2 Contemporary Methods in Ortho-Directed HIE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 280
3 Beyond Ortho-Directed HIE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286
3.1 Directed sp
3 C–H HIE Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 287
3.2 Non-ortho-HIE on Aromatic Substrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289
3.3 Vinyl HIE Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
3.4 Beyond C–H Labeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 292
4 Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 294
Abstract A history and summary of iridium-catalyzed hydrogen isotope exchange
(HIE) is described. Owing to the wide range of applications served by installation of
heavy and radioactive hydrogen isotopes, a wealth of synthetic labeling strategies
have been forthcoming. Principle among all HIE methods are those developed using
homogeneous iridium catalysts. This chapter covers major developments in (primarily homogeneous) iridium-centered catalysts for HIE. Connections to the broader
fields of hydrogenation and C–H functionalization are also considered.
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. Reid (*)
School of Chemistry, University of Bristol, Bristol, UK
e-mail: marc.reid@bristol.ac.uk
https://doi.org/10.1007/3418_2020_58
# The Author(s), under exclusive license to Springer Nature Switzerland AG 2020,
corrected publication 2020
Published online: 8 August 2020
Iridium Catalysts for Hydrogen Isotope
Exchange
Marc Reid
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 272
1.1 Isotopes and Isotopic Labeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 272
1.2 Applications of Hydrogen Isotope Exchange . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 273
1.3 Synthetic Methods in HIE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 273
2 Ortho-Directed Iridium-Catalyzed HIE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 274
2.1 Early Developments in Ortho-Directed HIE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 275
2.2 Contemporary Methods in Ortho-Directed HIE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 280
3 Beyond Ortho-Directed HIE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286
3.1 Directed sp
3 C–H HIE Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 287
3.2 Non-ortho-HIE on Aromatic Substrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289
3.3 Vinyl HIE Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
3.4 Beyond C–H Labeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 292
4 Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 294
Abstract A history and summary of iridium-catalyzed hydrogen isotope exchange
(HIE) is described. Owing to the wide range of applications served by installation of
heavy and radioactive hydrogen isotopes, a wealth of synthetic labeling strategies
have been forthcoming. Principle among all HIE methods are those developed using
homogeneous iridium catalysts. This chapter covers major developments in (primarily homogeneous) iridium-centered catalysts for HIE. Connections to the broader
fields of hydrogenation and C–H functionalization are also considered.
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. Reid (*)
School of Chemistry, University of Bristol, Bristol, UK
e-mail: marc.reid@bristol.ac.uk