Allylpalladium(II) Histidylidene Complexes and Their Application in Z-Selective Transfer Semihydrogenation of Alkynes

We have studied the use of amino acid histidine as a precursor for N‐heterocyclic carbene (NHC) ligands. This natural amino acid possesses an imidazole substituent, which makes it an interesting NHC precursor that contains both an acid and an amino functionality. These functionalities may be used fo...

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Bibliographic Details
Published in:European journal of inorganic chemistry 2015-02, Vol.2015 (6), p.982-996
Main Authors: Drost, Ruben M., Broere, Daniël L. J., Hoogenboom, Jorin, de Baan, Simone N., Lutz, Martin, de Bruin, B., Elsevier, C. J.
Format: Article
Language:English
Subjects:
Alkynes
Amino acids
Carbenes
Catalysis
Catalysts
Homogeneous catalysis
Hydrogenation
Ligands
Palladium
Palla­dium
Precursors
Reduction
Tuning
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Summary:We have studied the use of amino acid histidine as a precursor for N‐heterocyclic carbene (NHC) ligands. This natural amino acid possesses an imidazole substituent, which makes it an interesting NHC precursor that contains both an acid and an amino functionality. These functionalities may be used for further tuning of NHC complexes. We have developed routes for the synthesis of symmetric and dissymmetric alkyl, benzyl, and aryl‐substituted histidinium salts. Subsequently, the corresponding Ag and Pd histidylidenes were synthesized and the palladium complexes were tested in the Z‐selective transfer semihydrogenation of alkynes. Histidylidene palladium complexes that contain additional donor functionalities were found to display good selectivities. The best catalytic results were obtained with a Pd‐histidylidene complex that contains two picolyl functional groups. From an amino acid to versatile ligands and catalysts. Synthetic routes to histidinium salts and AgI and PdII histidylidenes were developed. The Pd‐histidylidenes were subsequently investigated in the transfer semihydrogenation of alkynes to Z‐alkenes
ISSN:1434-1948
1099-0682
DOI:10.1002/ejic.201403104