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Probing the ruthenium-catalyzed higher polyol hydrogenolysis reaction through the use of stereoisomers
Green Chemistry
  • Keenan Lee Deutsch, Iowa State University
  • Daniel George Lahr, Iowa State University
  • Brent H. Shanks, Iowa State University
Document Type
Article
Publication Version
Published Version
Publication Date
1-1-2012
DOI
10.1039/c2gc00026a
Abstract

Nine polyol stereoisomers ranging from three to six carbons in length were reacted under hydrogenolysis conditions (205-240°C, 100 bar H2) over a Ru-C catalyst to better understand the reaction mechanism. Previous reports have postulated the retro-aldol mechanism as the main pathway leading to C-C scission. However, the retro-aldol mechanism was insufficient in explaining the product distribution of tetritols from pentitols, while the decarbonylation mechanism could explain the selectivity results of terminal C-C scission. Retro-aldol scission of internal C-C bonds was confirmed to occur by the tetritol product distribution from hexitols. Therefore, the presence or role of 3-keto and 4-keto intermediates had a negligible effect on the C-C hydrogenolysis of polyols when compared to aldehyde intermediates. The reaction rates of the polyols depended on the configuration of the polyol stereoisomers. The reactivity of the stereoisomers was correlated to the presence of erythro sequences of hydroxyl groups and was independent of the carbon chain length.

Comments

This is an article from Green Chemistry 14 (2012): 1635, doi: 10.1039/c2gc00026a. Posted with permission.

Copyright Owner
The Royal Society of Chemistry
Language
en
Date Available
2015-03-11
File Format
application/pdf
Citation Information
Keenan Lee Deutsch, Daniel George Lahr and Brent H. Shanks. "Probing the ruthenium-catalyzed higher polyol hydrogenolysis reaction through the use of stereoisomers" Green Chemistry Vol. 14 Iss. 6 (2012) p. 1635 - 1642
Available at: http://works.bepress.com/brent_shanks/23/