N-Heterocyclic Carbene-Catalyzed Radical Relay Enabling Vicinal Alkylacylation of Alkenes
The N-heterocyclic carbene-catalyzed radical relay enables the vicinal alkylacylation of styrenes, acrylates and acrylonitrile using aldehydes and tertiary alkyl carboxylic acid-derived redox-active esters. This protocol introduces tertiary alkyl groups and acyl groups to C-C double bonds with complete regioselectivity to produce functionalized ketone derivatives. The radical relay mechanism involves single electron transfer from the enolate form of a Breslow intermediate and radical addition of the resultant alkyl radical to the alkene followed by radical-radical coupling.
N-Heterocyclic Carbene-Catalyzed Decarboxylative Alkylation of Aldehydes
We found that N-heterocyclic carbene catalysis promoted the unprecedented decarboxylative coupling of aryl aldehydes and tertiary or secondary alkyl carboxylic acid-derived redox-active esters to produce aryl alkyl ketones. The mild and transition-metal-free reaction conditions are attractive features of this method. The power of this protocol was demonstrated by the functionalization of pharmaceutical drugs and natural product. A reaction pathway involving single electron transfer from an enolate form of Breslow intermediate to a redox ester followed by recombination of the resultant radical pair to form a carbon-carbon bond is proposed.
Restricted rotation due to the lack of free space within a capsule translates into product selectivity: Photochemistry of cyclohexyl phenyl ketones within a water-soluble organic capsule
The rotational mobility of organic guest molecules when included within a confined capsule is restricted and this feature could be translated into product selectivity as established with the photochemical behavior of cyclohexyl phenyl ketones. The Royal Society of Chemistry.