854045-93-5Relevant articles and documents
Expanding Ligand Space: Preparation, Characterization, and Synthetic Applications of Air-Stable, Odorless Di- tert-alkylphosphine Surrogates
Barber, Thomas,Argent, Stephen P.,Ball, Liam T.
, p. 5454 - 5461 (2020)
The di-tert-alkylphosphino motif is common to many best-in-class ligands for late-transition-metal catalysis. However, the structural diversity of these privileged substructures is currently limited by the need to manipulate highly toxic, highly reactive reagents and intermediates in their synthesis. In response to this longstanding challenge, we report an umpolung strategy for the synthesis of structurally diverse di-tert-alkylphosphine building blocks via SN1 alkylation of in situ generated PH3 gas. We show that the products - which are isolated as air-stable, odorless phosphonium salts - can be used directly in the preparation of key synthetic intermediates and ligand classes. The di-tert-alkylphosphino building blocks that are accessible using our methodology therefore enable facile expansion of extant ligand classes by modification of a previously invariant vector; we demonstrate that these modifications affect the steric and electronic properties of the ligands and can be used to tune their performance in catalysis.
Synthesis, reactivity and catalytic activity of Au-PAd3complexes
Voloshkin, Vladislav A.,Saab, Marina,Van Hecke, Kristof,Lau, Sii Hong,Carrow, Bradley P.,Nolan, Steven P.
, p. 13872 - 13879 (2020/10/27)
Tri(1-adamantyl)phosphine (PAd3) possesses unique steric and electronic properties positioning it at the border between tertiary phosphines and N-heterocyclic carbenes (NHC). Novel Au-PAd3complexes were synthesized from the known [Au(PAd3)Cl]. We have optimised reaction conditions for the synthesis of this useful synthon in order to circumvent the formation of the [Au(PAd3)2]Cl. [Au(PAd3)Cl] was used to access a number of derivatives and some were deployed as catalysts. The hydration of alkynes was targeted to gauge the reactivity of Au-PAd3complexes and permit comparison with NHC and tertiary phosphine congeners.
Predicting Counterion Effects Using a Gold Affinity Index and a Hydrogen Bonding Basicity Index
Lu, Zhichao,Han, Junbin,Okoromoba, Otome E.,Shimizu, Naoto,Amii, Hideki,Tormena, Cláudio F.,Hammond, Gerald B.,Xu, Bo
supporting information, p. 5848 - 5851 (2017/11/10)
We have developed a gold affinity index and hydrogen bonding basicity index for counterions and have used these indexes to forecast their reactivity in cationic gold catalysis.
