Journal of Organic Chemistry
Journal of Organic Chemistry
5 years ago

Hypervalent-Iodine-Mediated Formation of Epoxides from Carbon(sp2)–Carbon(sp3) Single Bonds

Hypervalent-Iodine-Mediated Formation of Epoxides from Carbon(sp2)–Carbon(sp3) Single Bonds
Shan Jiang, Yong-Chao Han, Xiao-Song Xue, Li-Qian Cui, Chi Zhang, Tai-Shan Yan
We have developed an efficient method for direct formation of epoxide groups from carbon(sp2)–carbon(sp3) single bonds of β-keto esters; the reaction is mediated by the water-soluble hypervalent iodine(V) reagent AIBX (5-trimethylammonio-1,3-dioxo-1,3-dihydro-1λ5-benzo[d][1,2]iodoxol-1-ol anion). On the basis of the results of density functional theory calculations and experimental studies, we propose that the reaction proceeds by a two-stage mechanism involving dehydrogenation of the β-keto ester substrates and epoxidation of the resulting enone intermediates. The rate-limiting step is abstraction of the β′-C–H (calculated free energy of activation, 24.5 kcal/mol).

Publisher URL: http://dx.doi.org/10.1021/acs.joc.7b00883

DOI: 10.1021/acs.joc.7b00883

You might also like
Discover & Discuss Important Research

Keeping up-to-date with research can feel impossible, with papers being published faster than you'll ever be able to read them. That's where Researcher comes in: we're simplifying discovery and making important discussions happen. With over 19,000 sources, including peer-reviewed journals, preprints, blogs, universities, podcasts and Live events across 10 research areas, you'll never miss what's important to you. It's like social media, but better. Oh, and we should mention - it's free.

  • Download from Google Play
  • Download from App Store
  • Download from AppInChina

Researcher displays publicly available abstracts and doesn’t host any full article content. If the content is open access, we will direct clicks from the abstracts to the publisher website and display the PDF copy on our platform. Clicks to view the full text will be directed to the publisher website, where only users with subscriptions or access through their institution are able to view the full article.