期刊
ACS CATALYSIS
卷 11, 期 9, 页码 5452-5462出版社
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.1c01133
关键词
phosphenium ions; phosphirenium ions; organocatalysis; reaction mechanism studies; density functional theory; hydrosilylation
资金
- EPSRC
- Heriot Watt University
The utilization of phosphirenium ions as efficient pre-catalysts for metal-free carbonyl reduction with silanes is presented, alongside a detailed mechanistic study. The presence of electron-donating substituents on the phosphirenium cation favors off-cycle reactions, while electron-withdrawing substituents promote catalytic activity in hydrosilylation.
The utilization of phosphirenium ions is presented; optimized and broadened three-membered ring construction is described together with the use of these ions as efficient pre-catalysts for metal-free carbonyl reduction with silanes. Full characterization of the phosphirenium ions is presented, and initial experimental and computational mechanistic studies indicate that these act as a masked phosphenium source that is accessed via ring opening. Catalysis proceeds via associative transfer of {Ph2P+} to a carbonyl nucleophile, H-SiR3 bond addition over the C=O group, and associative displacement of the product by a further equivalent of the carbonyl substrate, which completes the catalytic cycle. A competing off-cycle process leading to vinyl phosphine formation is detailed for the hydrosilylation of benzophenone for which an inverse order in [silane] is observed. Experimentally, the formation of side products, including off-cycle vinyl phosphine, is favored by electron-donating substituents on the phosphirenium cation, while catalytic hydrosilylation is promoted by electron-withdrawing substituents. These observations are rationalized in parallel computational studies.
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