Light-Driven, Zirconium-Catalyzed Hydrophosphination with Primary Phosphines
| Autor: | Elizabeth R. Young, Rory Waterman, Christine A. Bange, Matthew A. Conger, Matthew D. Liptak, Bryan T. Novas |
|---|---|
| Rok vydání: | 2018 |
| Předmět: |
Zirconium
010405 organic chemistry Chemistry Photodissociation chemistry.chemical_element Substrate (chemistry) General Chemistry 010402 general chemistry Photochemistry medicine.disease_cause 01 natural sciences Catalysis 0104 chemical sciences Photoexcitation Intramolecular force Photocatalysis medicine Ultraviolet |
| Zdroj: | ACS Catalysis. 8:6230-6238 |
| ISSN: | 2155-5435 |
| Popis: | Catalytic hydrophosphination using [κ5-N,N,N,N,C-(Me3SiNCH2CH2)2NCH2CH2NSiMe2CH2]Zr (1) under photolysis substantially enhances activity and avails greater substrate scope. Quantitative conversions of alkenes to secondary phosphines are reached in as little as 20 min at ambient temperature with 1 under ultraviolet or visible irradiation. A larger class of unactivated alkenes are now facile substrates under photolysis conditions, and 1 can engage in a previously unknown tandem inter/intramolecular hydrophosphination of 1,4-pentadiene to give the heterocyclic phosphorinane product. Computational and spectroscopic data indicate that photoexcitation of 1 at a variety of wavelengths results in P n → Zr d charge transfer. This excitation appears to accelerate catalysis by promoting substrate insertion at the Zr–P bond based on experimental observations. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|