A practical free-radical approach to 1,4-dicarbonyl compounds

Published Date

15 April 2015, Vol.71(15):2234–2240, doi:10.1016/j.tet.2015.02.077

Title 

A practical free-radical approach to 1,4-dicarbonyl compounds

Dedicated to the memory of Professor Eugene A. Bratoeff

• Author 

• Eduardo Peralta-Hernández ^†
• Ever A. Blé-González ^†
• Víctor A. Gracia-Medrano-Bravo
• Alejandro Cordero-Vargas ^,

• Instituto de Química, Universidad Nacional Autónoma de México, Circuito Exterior s/n, Ciudad Universitaria, 04510 México D.F., Mexico

Received 10 December 2014. Revised 19 February 2015. Accepted 23 February 2015. Available online 26 February 2015.

Abstract
A practical radical/ionic sequence based on the addition of electrophilic radicals onto vinyl acetates, is described. The addition of such radicals, derived from commercially available iodoesthers, iodonitriles or iodoacetamides onto enol acetates generates the atom transfer adduct—a geminal halohydrine acetate—which is unstable and therefore promotes the ionic elimination of the transferred iodine to thus regenerate the carbonyl compound. This simple protocol provides a broad variety of 1,4-dicarbonyl compounds (or equivalents), such as ketoaldehydes, ketoesters, ketonitriles, and formylnitriles.

Graphical abstract

Keywords

• Free radicals
• Radical-ionic sequence
• Vinyl acetates
• 1,4-Dicarbonyl compounds
• Octahydroindole

---

Scheme 1.

Scheme 2.

Scheme 3.

 Table 1

Table 1.

 Table 2

Table 2.

Scheme 4.

 Table 3

Table 3.

Scheme 5.

Scheme 6.

Scheme 7.

Scheme 8.

• DOCX (35.8M)

• ∗ 
  Corresponding author. Tel.: +52 55 56224450; fax: +52 55 56162217.

For further details log on website :
http://www.sciencedirect.com/science/article/pii/S0040402015002586