Catch It If You Can: Copper-Catalyzed (Transfer) Hydrogenation Reactions and Coupling Reactions by Intercepting Reactive Intermediates Thereof

Lea T. Brechmann; Johannes F. Teichert

doi:10.1055/s-0040-1707185

Synthesis, Table of Contents

Synthesis 2020; 52(17): 2483-2496
DOI: 10.1055/s-0040-1707185

short review

Catch It If You Can: Copper-Catalyzed (Transfer) Hydrogenation Reactions and Coupling Reactions by Intercepting Reactive Intermediates Thereof

Lea T. Brechmann

,

Johannes F. Teichert ∗

Institut für Chemie, Technische Universität Berlin, Straße des 17. Juni 115, 10623 Berlin, Germany Email: johannes.teichert@chem.tu-berlin.de

› Author Affiliations

Abstract

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Abstract

The key reactive intermediate of copper(I)-catalyzed alkyne semihydrogenations is a vinylcopper(I) complex. This intermediate can be exploited as a starting point for a variety of trapping reactions. In this manner, an alkyne semihydrogenation can be turned into a dihydrogen-mediated coupling reaction. Therefore, the development of copper-catalyzed (transfer) hydrogenation reactions is closely intertwined with the corresponding reductive trapping reactions. This short review highlights and conceptualizes the results in this area so far, with H₂-mediated carbon–carbon and carbon–heteroatom bond-forming reactions emerging under both a transfer hydrogenation setting as well as with the direct use of H₂. In all cases, highly selective catalysts are required that give rise to atom-economic multicomponent coupling reactions with rapidly rising molecular complexity. The coupling reactions are put into perspective by presenting the corresponding (transfer) hydrogenation processes first.

1 Introduction: H₂-Mediated C–C Bond-Forming Reactions

2 Accessing Copper(I) Hydride Complexes as Key Reagents for Coupling Reactions; Requirements for Successful Trapping Reactions

3 Homogeneous Copper-Catalyzed Transfer Hydrogenations

4 Trapping of Reactive Intermediates of Alkyne Transfer Semihydrogenation Reactions: First Steps Towards Hydrogenative Alkyne Functionalizations

5 Copper(I)-Catalyzed Alkyne Semihydrogenations

6 Copper(I)-Catalyzed H₂-Mediated Alkyne Functionalizations; Trapping of Reactive Intermediates from Catalytic Hydrogenations

6.1 A Detour: Copper(I)-Catalyzed Allylic Reductions, Catalytic Generation of Hydride Nucleophiles from H₂

6.2 Trapping with Allylic Electrophiles: A Copper(I)-Catalyzed Hydroallylation Reaction of Alkynes

6.3 Trapping with Aryl Iodides

7 Conclusion

Key words

cross-coupling - dihydrogen - copper - catalysis - alkynes

Full Text

References

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