Acid-catalyzed acylation reaction via C-C bond cleavage: A facile and mechanistically defined approach to synthesize 3-acylindoles
A facile acid-catalyzed acylation of indoles with 1,3-dione as an eco-friendly acylating agent was developed. This protocol combines C-C bond cleavage and heterocyclic C-H bond functionalization to form new C-C bonds. Based on the detailed mechanistic studies, a credible mechanistic pathway was proposed. This journal is
One-pot desulfonylative alkylation of N-sulfonyl azacycles using alkoxides generated by phase-transfer catalysis
Sulfonamide heterocycles, specifically 3-acylindoles, undergo a deprotection/alkylation sequence in the presence of an appropriate alcohol when cesium carbonate or potassium carbonate and a phase-transfer catalyst are utilized. The outcome of the one-pot protocol was found to be significantly dependent on both the alcohol and sulfonamide heterocycle employed. Strictly anhydrous conditions are not necessary for this protocol. Georg Thieme Verlag Stuttgart · New York.
Denton, Justin R.
scheme or table
p. 775 - 782
(2010/09/11)
Modulating reactivity and diverting selectivity in palladium-catalyzed heteroaromatic direct arylation through the use of a chloride activating/blocking group
(Chemical Equation Presented) Through the introduction of an aryl chloride substituent, the selectivity of palladium-catalyzed direct arylation may be diverted to provide alternative regioisomeric products in high yields. In cases where low reactivity is typically observed, the presence of the carbon-chlorine bond can serve to enhance reactivity and provide superior outcomes. From a strategic perspective, the C-Cl bond is easily introduced and can be employed in a variety of subsequent transformations to provide a wealth of highly functionalized heterocycles with minimal substrate preactivation. The impact of the C-Cl functional group on direct arylation reactivity has also been evaluated mechanistically, and the observed reactivity profiles correlate very well with that predicted by a concerted metalation-deprotonation pathway.
Liegault, Benoit,Petrov, Ivan,Gorelsky, Serge I.,Fagnou, Keith
supporting information; experimental part
p. 1047 - 1060
(2010/04/04)
Towards the syntheses of N-H and N-alkylated derivatives of meridianins
(Chemical Equation Presented) Novel N-H and N-alkylated derivatives of meridianins have been synthesized as potential antitumor agents by a two-step conversion of N-tosyl-3-acetylindoles or N-alkyl-3-acetylindoles to the corresponding enaminones using DMF-DMA, with or without added pyrrolidine. Further cyclization with guanidine gave the corresponding 2-aminopyrimidines. The structures of the compounds, thus obtained, were proved by 1H and 13C NMR spectroscopy, NOE experiments and X-ray analysis.