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

Title
Support for a Dioxyallyl Cation in the Mechanism Leading to (−)-Levoglucosenone
Publication Date
2017
Author(s)
Greatrex, Ben
( author )
OrcID: https://orcid.org/0000-0002-0356-4966
Email: bgreatre@une.edu.au
UNE Id une-id:bgreatre
Meisner, Jan
Glover, Stephen
( author )
OrcID: https://orcid.org/0000-0002-9344-8669
Email: sglover@une.edu.au
UNE Id une-id:sglover
Raverty, Warwick
Type of document
Journal Article
Language
en
Entity Type
Publication
Publisher
American Chemical Society
Place of publication
United States of America
DOI
10.1021/acs.joc.7b02109
UNE publication id
une:22968
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.
Link
Citation
The Journal of Organic Chemistry, 82(23), p. 12294-12299
ISSN
1520-6904
0022-3263
Start page
12294
End page
12299

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