One-Metal/Two-Ligand for Dual Activation Tandem Catalysis: Photoinduced Cu-Catalyzed Anti-hydroboration of Alkynes
| Autor: | Corpas, Javier, Gomez-Mendoza, Miguel, Ramírez-Cárdenas, Jonathan, de la Peña O’Shea, Víctor A., Mauleón, Pablo, Gómez Arrayás, Ramón, Carretero, Juan C. |
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| Rok vydání: | 2022 |
| Předmět: | |
| Zdroj: | Biblos-e Archivo. Repositorio Institucional de la UAM instname |
| ISSN: | 1520-5126 |
| Popis: | A dual catalyst system based on ligand exchange of two diphosphine ligands possessing different properties in a copper complex has been devised to merge metal- and photocatalytic activation modes. This strategy has been applied to the formal anti-hydroboration of activated internal alkynes via a tandem sequence in which Cu/Xantphos catalyzes the B2pin2-syn-hydroboration of the alkyne whereas Cu/BINAP serves as a photocatalyst for visible light-mediated isomerization of the resulting alkenyl boronic ester. Photochemical studies by means of UV–vis absorption, steady-state and time-resolved fluorescence, and transient absorption spectroscopy have allowed characterizing the photoactive Cu/BINAP species in the isomerization reaction and its interaction with the intermediate syn-alkenyl boronic ester through energy transfer from the triplet excited state of the copper catalyst. In addition, mechanistic studies shed light into catalyst speciation and the interplay between the two catalytic cycles as critical success factors. We thank the Ministerio de Ciencia e Innovación (MICINN) and Fondo Europeo de Desarrollo Regional (FEDER, UE) forfinancial support (Agencia Estatal de Investigación/Project PGC2018-098660-B-I00). J.C.C. thanks MECD for a FPU fellowship. Financial support was received from AEI-MICINN/FEDER, UE through the Nympha Project (PID2019-106315RB-I00). |
| Databáze: | OpenAIRE |
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