114615-82-6Relevant articles and documents
Hydrogen-Bonding Interactions in the Ley–Griffith Oxidation: Practical Considerations for the Synthetic Chemist
Moore, Peter W.,Zerk, Timothy J.,Burns, Jed M.,Bernhardt, Paul V.,Williams, Craig M.
, p. 303 - 308 (2019)
The Ley–Griffith oxidation, which is catalyzed by tetra-n-propylammonium perruthenate (TPAP, nPr4N[RuO4]), is a popular method for not only controlled oxidation of primary alcohols to aldehydes, but also a host of other synthetically useful transformations. While the fundamental reaction mechanism has recently been elucidated, several key hydrogen-bonding interactions between the reagents were implicated but not investigated. Herein the prevalence of H-bonding between the co-oxidant N-methylmorpholine N-oxide (NMO), the alcohol substrate, water and the perruthenate catalyst is established. These observations help to rationalize the importance of drying the reagents and lead to several practical suggestions.
N -Oxides rescue Ru(v) in catalytic Griffith-Ley (TPAP) alcohol oxidations
Zerk, Timothy J.,Moore, Peter W.,Williams, Craig M.,Bernhardt, Paul V.
, p. 10301 - 10304 (2016)
The redox and ligand exchange reactions of oxido-ruthenium complexes are central to the function of the Sharpless and Griffith-Ley one-step alcohol oxidation protocols. However, their mechanisms have not been elucidated. Cyclic voltammetry and UV-vis spec
ATP3 and MTP3: Easily Prepared Stable Perruthenate Salts for Oxidation Applications in Synthesis
Moore, Peter W.,Read, Christopher D. G.,Bernhardt, Paul V.,Williams, Craig M.
supporting information, p. 4556 - 4561 (2018/03/13)
The Ley–Griffith tetra-n-propylammonium perruthenate (TPAP) catalyst has been widely deployed by the synthesis community, mainly for the oxidation of alcohols to aldehydes and ketones, but also for a variety of other synthetic transformations (e.g. diol cleavage, isomerizations, imine formation and heterocyclic synthesis). Such popularity has been forged on broad reaction scope, functional group tolerance, mild conditions, and commercial catalyst supply. However, the mild instability of TPAP creates preparation, storage, and reaction reproducibility issues, due to unpreventable slow decomposition. In search of attributes conducive to catalyst longevity an extensive range of novel perruthenate salts were prepared. Subsequent evaluation unearthed a set of readily synthesized, bench stable, phosphonium perruthenates (ATP3 and MTP3) that mirror the reactivity of TPAP, but avoid storage decomposition issues.