These tools will no longer be maintained as of December 31, 2024. Archived website can be found here. PubMed4Hh GitHub repository can be found here. Contact NLM Customer Service if you have questions.


Pubmed for Handhelds

PUBMED FOR HANDHELDS

Search MEDLINE/PubMed

  • Title: Direct Umpolung Morita-Baylis-Hillman like α-Functionalization of Enones via Enolonium Species.
    Author: Arava S, Santra SK, Pathe GK, Kapanaiah R, Szpilman AM.
    Journal: Angew Chem Int Ed Engl; 2020 Aug 24; 59(35):15171-15175. PubMed ID: 32394609.
    Abstract:
    Herein we report on the umpolung of Morita-Baylis-Hillman type intermediates and application to the α-functionalization of enone C-H bonds. This reaction gives direct access to α-chloro-enones, 1,2-diketones and α-tosyloxy-enones. The latter are important intermediates for cross-coupling reaction and, to the best of our knowledge, cannot be made in a single step from enones in any other way. The proposed mechanism is supported by spectroscopic studies. The key initial step involves conjugate attack of an amine (DABCO or pyridine), likely assisted by hypervalent iodine acting as a Lewis acid leading to formation of an electrophilic β-ammonium-enolonium species. Nucleophilic attack by acetate, tosylate, or chloride anion is followed by base induced elimination of the ammonium species to give the noted products. Hydrolysis of α-acetoxy-enones lead to formation of 1,2-diketones. The α-tosyl-enones participate in Negishi coupling reactions under standard conditions.
    [Abstract] [Full Text] [Related] [New Search]