Sodium iodide-catalyzed direct α-alkoxylation of ketones with alcohols via oxidation of α-iodo ketone intermediates
The direct α-alkoxylation of ketones with alcohols via a sodium iodide-catalyzed oxidative cross-coupling has been developed. This protocol enables a range of alkyl aryl ketones to cross couple with an array of alcohols in synthetically useful yields. The mechanistic studies provided solid evidence supporting that an α-iodo ketone was a key reaction intermediate, being converted into an α-alkoxylated ketone via further oxidation to a hypervalent iodine species rather than a common nucleophilic substitution, and was generated from the ketone starting material via a radical intermediate. These new mechanism insights should have an effect on the design of iodide-catalyzed oxidative cross-coupling reactions between nucleophiles.
A facile synthesis of secondary α-alkoxy or α-acetoxy aromatic ketones
The treatment of HNIB with aromatic ketones and subsequent solvolysis using alcohol or acetic acid in one-pot system makes it possible to give corresponding secondary α-alkoxy or α-acetoxy ketones in high yields.
Lee, Jong Chan,Hong, Taiyoung
p. 4085 - 4090
(2007/10/03)
Photochemistry of substituted propiophenones: An interesting α-and aryl substituents effect on their photobehaviour
Photochemistry of different α-substituted and phenyl-substituted propiophenones in methanol is investigated with a view to delineate the substituent effect with a special reference tu their rearrangement to α-arylpropanoic acids, an important class of nonsteroidal antiinflammatory agents. The results thus obtained bringsforth an important element of their reactivityprofile i.e. the α-chloro-substituent in combination with nuclear alkyl substituents (para>meta) favours 1,2-arylmigration leading to the synthetically useful reaction for α-arylpro panoic acids.