Lemieux-von Rudloff oxidation

Fig. 14.23. The Ru04 cleavage of a phenyl ring is exemplified by the case of an alkylated aromatic compound using the modified Lemieux-von Rudloff conditions (Figure 14.20). The reaction involves two key intermediates the a-ketoaldehyde A and the ruthenium(VIII) acid diester D. The mechanism for the reaction of A to D is not known. Diester D fragments and forms a substituted acetic acid, Ru03, and formic acid in the last step via a cyclic transition state. Under the reaction conditions, formic acid is oxidized further to...

S-8-S carbon skeleton of Aisicoccins and ophiobolins (equation 10). Trisubstituted alkenes yield keto acids (equation 11). A related reaction, known as the Lemieux-von Rudloff (periodate-permanganate) oxidation, is also used to oxidize alkenes to acids or ketones (equation 12). If aldehydes are required... 

Li et al. developed a simple and versatile strategy for converting hydrophobic rare earth nanophosphors into water-soluble and carboxylic acid-functionalized analogues. The surface oleic acid ligands could be directly oxidized by the Lemieux-von Rudloff reagent, and the modified NCs kept the excellent luminescence and were further used as DNA labels (Figure 77) (Chen et al., 2008c). 

Figure 1339 Surface ligand oxidation strategy for synthesis of functionalized oleic acid-capped UCNPs. (a) Direct oxidization with the Lemieux-von Rudloff reagent and (b) epoxidation and further coupling with mPEG-OH.

Periodate-Permanganate oxidation [1, 810-812, at end]. In carrying out the oxidation of (R)-(+)-citronellol (8) to the 6-hydroxy-4-methylhexanoic acid (9) by the Lemieux-von Rudloff reagent, Overberger and Kaye16 used acetone-water as the medium in order to conduct the oxidation at a higher concentration. 

Scheme 2 Schematic illustration of a ligand oxidation process. Surface capping oleic acid molecules were oxidized by a Lemieux-von Rudloff reagent. (Reproduced with permission from Ref 58. Copyri t (2008) American Chemical Society.)...

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