5581-75-9Relevant articles and documents
Evidence for the involvement of silver nanoclusters during the wolff rearrangement of α-diazoketones
Sudrik, Surendra G.,Maddanimath, Trupti,Chaki, Nirmalya K.,Chavan, Sambhaji P.,Chavan, Subhash P.,Sonawane, Harikisan R.,Vijayamohanan
, p. 2355 - 2358 (2003)
(Matrix presented) In situ-generated silver nanoclusters(Agn) during the reduction of either silver(I) oxide or other salts presumably catalyze the Wolff rearrangement of α-diazoketones. Their optical, physical, and catalytic properties depend
Site-Selective, Remote sp3 C?H Carboxylation Enabled by the Merger of Photoredox and Nickel Catalysis
Sahoo, Basudev,Bellotti, Peter,Juliá-Hernández, Francisco,Meng, Qing-Yuan,Crespi, Stefano,K?nig, Burkhard,Martin, Ruben
supporting information, p. 9001 - 9005 (2019/06/24)
A photoinduced carboxylation of alkyl halides with CO2 at remote sp3 C?H sites enabled by the merger of photoredox and Ni catalysis is described. This protocol features a predictable reactivity and site selectivity that can be modulated by the ligand backbone. Preliminary studies reinforce a rationale based on a dynamic displacement of the catalyst throughout the alkyl side chain.
Synthetic Applications and Mechanistic Studies of the Hydroxide-Mediated Cleavage of Carbon-Carbon Bonds in Ketones
Mazziotta, Andrea,Makarov, Ilya S.,Fristrup, Peter,Madsen, Robert
, p. 5890 - 5897 (2017/06/07)
The hydroxide-mediated cleavage of ketones into alkanes and carboxylic acids has been reinvestigated and the substrate scope extended to benzyl carbonyl compounds. The transformation is performed with a 0.05 M ketone solution in refluxing xylene in the presence of 10 equiv of potassium hydroxide. The reaction constitutes a straightforward protocol for the synthesis of certain phenyl-substituted carboxylic acids from 2-phenylcycloalkanones. The mechanism was investigated by kinetic experiments which indicated a first order reaction in hydroxide and a full negative charge in the rate-determining step. The studies were complemented by a theoretical investigation where two possible pathways were characterized by DFT/M06-2X. The calculations showed that the scission takes place by nucleophilic attack of hydroxide on the ketone followed by fragmentation of the resulting oxyanion into the carboxylic acid and a benzyl anion.