Greatrex, Ben; Meisner, Jan; Glover, Stephen; Raverty, Warwick

Author(s)

Greatrex, Ben

Meisner, Jan

Glover, Stephen

Raverty, Warwick

Publication Date

2017

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.

Citation

The Journal of Organic Chemistry, 82(23), p. 12294-12299

ISSN

1520-6904

0022-3263

Link

https://hdl.handle.net/1959.11/22784

Publisher

American Chemical Society

Title

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

Type of document

Journal Article

Entity Type

Publication

Author(s)	Greatrex, Ben Meisner, Jan Glover, Stephen Raverty, Warwick
Publication Date	2017
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.
Citation	The Journal of Organic Chemistry, 82(23), p. 12294-12299
ISSN	1520-6904 0022-3263
Link	https://hdl.handle.net/1959.11/22784
Publisher	American Chemical Society
Title	Support for a Dioxyallyl Cation in the Mechanism Leading to (−)-Levoglucosenone
Type of document	Journal Article
Entity Type	Publication

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

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