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Synthesis 2020; 52(17): 2483-2496
DOI: 10.1055/s-0040-1707185
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
This work was supported by the Deutsche Forschungsgemeinschaft (DFG) (German Research Council) (Emmy Noether Fellowship for J.F.T., TE1101/2-1) and by the Fonds der Chemischen Industrie (Liebig-Stipendium for J.F.T.).Further Information
Publication History
Received: 21 May 2020
Accepted after revision: 18 June 2020
Publication Date:
13 July 2020 (online)
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
-
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For reviews, see:
For selected examples, see:
For reductive and borylative alkyne functionalizations, see:
Closely related to the reductive alkyne functionalizations presented here are the corresponding borylative transformations. For reviews, see:
For selected examples, see:
For reviews on copper(I) hydride chemistry, see:
For the rare use of other hydride donors in copper(I) hydride chemistry, see:
As an alternative, copper(I) hydrides can be formed directly from copper(II) acetate and a hydrosilane, without addition of an alkoxide as activator. The mechanistic basis for this process has not been studied. For examples, see:
For reviews on transfer hydrogenation, see:
For reviews on copper(I)/NHC complexes, see:
For reviews on alkyne semihydrogenation, see:
A similar influence of the alkene geometry on the outcome of the catalytic reaction has also been observed in related reactions, see:
For reviews on copper(I)-catalyzed allylic substitutions, see:
For related three-component reactions employing hydrosilanes as the hydride source, see: