37562-71-3Relevant academic research and scientific papers
Light-Driven Carbene Catalysis for the Synthesis of Aliphatic and α-Amino Ketones
Bay, Anna V.,Cheong, Paul Ha-Yeon,Farah, Abdikani Omar,Fitzpatrick, Keegan P.,González-Montiel, Gisela A.,Scheidt, Karl A.
, p. 17925 - 17931 (2021/07/17)
Single-electron N-heterocyclic carbene (NHC) catalysis has gained attention recently for the synthesis of C?C bonds. Guided by density functional theory and mechanistic analyses, we report the light-driven synthesis of aliphatic and α-amino ketones using single-electron NHC operators. Computational and experimental results reveal that the reactivity of the key radical intermediate is substrate-dependent and can be modulated through steric and electronic parameters of the NHC. Catalyst potential is harnessed in the visible-light driven generation of an acyl azolium radical species that undergoes selective coupling with various radical partners to afford diverse ketone products. This methodology is showcased in the direct late-stage functionalization of amino acids and pharmaceutical compounds, highlighting the utility of single-electron NHC operators.
The Willgerodt-Kindler Reactions. 6. Isomerization of the Carbonyl Group in Alkanones and Cycloalkanones
Carmack, Marvin,Behforouz, Mohammad,Berchtold, Glenn A.,Berkowitz, Samuel M.,Wiesler, Donald,Barone, Ralph
, p. 1305 - 1318 (2007/10/02)
The most unusual feature of the Willgerodt-Kindler Reactions is the facile isomerization of the carbonyl function along a chain of unbranched methylene groups, or around a cycloaliphatic ring containing several connected methylene groups.We have demonstrated that the first step in the Kindler process is the formation of enamines by reaction of the carbonyl function with secondary aliphatic amines, followed by reaction of the enamine with certain sulfur-amine catalysts to form reactive heterocyclic sulfur intermediates that facilitate the elimination-readdition of the amines reversibly along the chain.It was shown that compounds of the type R2N-S-S-NR2 are effective catalysts but not compounds of the type R2N-S-NR2.Some cyclohexanone derivatives undergo aromatization, with anomalous results in certain cases.
