Please use this identifier to cite or link to this item:
https://hdl.handle.net/1959.11/22784
Title: | Support for a Dioxyallyl Cation in the Mechanism Leading to (−)-Levoglucosenone | Contributor(s): | Greatrex, Ben (author) ; Meisner, Jan (author); Glover, Stephen (author) ; Raverty, Warwick (author) | Publication Date: | 2017 | DOI: | 10.1021/acs.joc.7b02109 | Handle Link: | https://hdl.handle.net/1959.11/22784 | Abstract: | 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. | Publication Type: | Journal Article | Source of Publication: | The Journal of Organic Chemistry, 82(23), p. 12294-12299 | Publisher: | American Chemical Society | Place of Publication: | United States of America | ISSN: | 1520-6904 0022-3263 |
Fields of Research (FoR) 2008: | 030505 Physical Organic Chemistry 030504 Organic Green Chemistry 030503 Organic Chemical Synthesis |
Fields of Research (FoR) 2020: | 340505 Physical organic chemistry 340504 Organic green chemistry 340503 Organic chemical synthesis |
Socio-Economic Objective (SEO) 2008: | 970103 Expanding Knowledge in the Chemical Sciences | Socio-Economic Objective (SEO) 2020: | 280105 Expanding knowledge in the chemical sciences | Peer Reviewed: | Yes | HERDC Category Description: | C1 Refereed Article in a Scholarly Journal |
---|---|
Appears in Collections: | Journal Article School of Rural Medicine School of Science and Technology |
Files in This Item:
File | Description | Size | Format |
---|
Items in Research UNE are protected by copyright, with all rights reserved, unless otherwise indicated.