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Article
Computational and NMR Spectroscopic Evidence for Stereochemistry-Dependent Conformations of 2,2,6,6-Tetramethylpiperidinyl-Masked 1,2-Diols
The Journal of Organic Chemistry
  • Eliscia Fought, Iowa State University
  • Shreyosree Chatterjee, Iowa State University
  • Theresa Lynn Windus, Iowa State University
  • Jason Chen, Iowa State University
Document Type
Article
Publication Version
Published Version
Publication Date
1-1-2015
DOI
10.1021/acs.joc.5b01516
Abstract
2,2,6,6-Tetramethylpiperidinyl-masked 1,2-diols exhibited stereochemistry-dependent hydroxyl proton chemical shifts: ca. 7 ppm for the syn diastereomer and ca. 2 ppm for the anti diastereomer. A computational search for low energy geometries revealed that the syn isomer favors a six-membered ring hydrogen bond to nitrogen and the anti isomer favors a five-membered ring hydrogen bond to oxygen. The computed low energy conformations were found to have a large difference in hydroxyl proton shielding that was reflected in the experimental chemical shift difference. This chemical shift difference was observed in a broad range of solvents, and thus may be useful as a stereochemical probe. The stereochemistry-dependent conformation and chemical shift signature appeared to be due to a syn pentane interaction between the gem-dimethyl groups on the 2,2,6,6-tetramethylpiperidinyl moiety.
Comments

Reprinted (adapted) with permission from J. Org. Chem., 2015, 80 (20), pp 9967–9972. Copyright 2015 American Chemical Society.

Copyright Owner
American Chemical Society
Language
en
File Format
application/pdf
Citation Information
Eliscia Fought, Shreyosree Chatterjee, Theresa Lynn Windus and Jason Chen. "Computational and NMR Spectroscopic Evidence for Stereochemistry-Dependent Conformations of 2,2,6,6-Tetramethylpiperidinyl-Masked 1,2-Diols" The Journal of Organic Chemistry Vol. 80 Iss. 20 (2015) p. 9967 - 9972
Available at: http://works.bepress.com/jason-shih-hao-chen/3/