73188-49-5Relevant academic research and scientific papers
Umpolung Strategy for α-Functionalization of Aldehydes for the Addition of Thiols and other Nucleophiles
Blom, Jakob,Reyes-Rodríguez, Gabriel J.,Tobiesen, Henriette N.,Lamhauge, Johannes N.,Iversen, Marc V.,Barl?se, Casper L.,Hammer, Niels,Rusbjerg, Matilde,J?rgensen, Karl Anker
, p. 17856 - 17862 (2019/11/13)
Nucleophile–nucleophile coupling is a challenging transformation in organic chemistry. Herein we present a novel umpolung strategy for α-functionalization of aldehydes with nucleophiles. The strategy uses organocatalytic enamine activation and quinone-promoted oxidation to access O-bound quinol-intermediates that undergo nucleophilic substitution reactions. These quinol-intermediates react with different classes of nucleophiles. The focus is on an unprecedented organocatalytic oxidative α-thiolation of aldehydes. The reaction scope is demonstrated for a broad range of thiols and extended to chemoselective bioconjugation, and applicable to a large variety of aldehydes. This strategy can also encompass organocatalytic enantioselective coupling of α-branched aldehydes with thiols forming quaternary thioethers. Studies indicate a stereoselective formation of the intermediate followed by a stereospecific nucleophilic substitution reaction at a quaternary stereocenter, with inversion of configuration.
A novel synthesis of α-(phenylthio)aldehydes
Jansen, B. J. M.,Peperzak, R. M.,Groot, Ae. de
, p. 489 - 494 (2007/10/02)
Addition of methoxy(phenylthio)methyllithium to ketones, followed by rearrangement of the adducts, provides a new method for the preparation of α-(phenylthio)aldehydes.The rearrangement is stereospecific.
A NOVEL SYNTHESIS OF α-SULFENYLATED ALDEHYDES
Groot, Ae. de,Jansen, B. J. M.
, p. 887 - 888 (2007/10/02)
Ketones are converted into α-sulfenylated aldehydes with addition of one carbon atom via reaction with methoxyphenylthiomethyllithium followed by rearrangement of the adducts.
