Journal of Organic Chemistry
Journal of Organic Chemistry
5 years ago

Support for a Dioxyallyl Cation in the Mechanism Leading to (−)-Levoglucosenone

Support for a Dioxyallyl Cation in the Mechanism Leading to (−)-Levoglucosenone
Jan Meisner, Ben W. Greatrex, Warwick Raverty, Stephen A. Glover
Levoglucosenone (LGO) is the major product formed when cellulose is pyrolyzed in the presence of acid at temperatures between 170 and 350 °C. The current intense interest in biomass conversion has led to a number of reports on its preparation; however, there is still uncertainty on the mechanism leading to LGO. We propose a new mechanism which involves a C2–C1 hydride shift followed by intramolecular trapping of a dioxyallyl cation. The reaction has been modeled using DFT calculations from the known LGO precursors levoglucosan and 1,4:3,6-dianhydro-α-D-glucopyranose to a common intermediate with calculated barriers of 10.6 and 13.5 kcal·mol–1, respectively. A discussion of the literature on the formation of LGO from late pathway intermediates is also provided.

Publisher URL: http://dx.doi.org/10.1021/acs.joc.7b02109

DOI: 10.1021/acs.joc.7b02109

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.