Direct α-Iodination of Aryl Alkyl Ketones by Elemental Iodine Activated by 1-Chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane Bis(tetrafluoroborate)

Marjan Jereb; Stojan Stavber; Marko Zupan

doi:10.1055/s-2003-38689

PAPER

Direct α-Iodination of Aryl Alkyl Ketones by Elemental Iodine Activated by 1-Chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane Bis(tetrafluoroborate)

Marjan Jereb, Stojan Stavber*, Marko Zupan
Laboratory for Organic and Bioorganic Chemistry, ‘Jozef Stefan’ Institute and Department of Chemistry, University of Ljubljana, Jamova 39, 1000 Ljubljana, Slovenia
Fax: +386(1)4773811; e-Mail: stojan.stavber@ijs.si;

Abstract

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Abstract

Selective introduction of an iodine atom at the α-carbonyl position in various aryl alkyl ketones was effectively achieved by reaction of target molecules with elemental iodine in the presence of N-F reagents. The best results were obtained by using 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate) (Selectfluor^Τ ^Μ F-TEDA-BF₄) as the iodination mediator and methanol as the solvent. Despite a strongly activated aromatic ring, iodomethyl derivatives were thus exclusively obtained from the corresponding hydroxy and methoxy substituted acetophenone derivatives, 3-acetylindole and 2-acetylbenzofuran, while the α-iodo derivative was the main product in the case of iodination of 1,5,6,7-tetrahydro-4H-indol-4-one and 6,7-dihydro-1-benzothiophene-4(5H)-one.

Key words

iodine - ketones - regioselectivity - fluorine

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