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Nuclear Magnetic Resonance Spectroscopy. Carbon-13 Chemical Shifts in Norbornyl Derivatives

Roberts, John D. and Grutzner, John B. and Jautelat, Manfred. and Dence, Joseph B. and Smith, Robert A. (1970) Nuclear Magnetic Resonance Spectroscopy. Carbon-13 Chemical Shifts in Norbornyl Derivatives. Journal of the American Chemical Society, 92 (24). pp. 7107-7120. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20151012-133440486

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Abstract

The ^(13)C chemical shifts for a number of norbornyl derivatives have been obtained in natural abundance. The compounds studied were the series of methylnorbornanes, methylnorbornenes, methyl-2-norbornanones, methyl-2,2-difluoronorbornanes, and a variety of exo- and endo-2-substituted norbornanes. The observed shifts have been interpreted in terms of inductive, bond length, and steric effects. The ɑ- and β-substituent effects are shown to be dependent on the extent of substitution at both the α and β carbon atoms and changes in bond lengths have been used to rationalize the shift changes. Steric interactions between the endo-2 and endo-6 positions, and the exo-2 and syn-7 positions have been shown to generate important chemical- shift changes and these changes can be used as a semiquantitative measure of steric interactions in norbornyl derivatives. Studies with electron-withdrawing groups have revealed a new long-range cmr y effect produced by exo-2 substituents on C-6. These shifts appear to provide a sensitive and quantitative measure of the electronic demands of a neighboring group as a function of stereochemistry. The substituent shifts obtained from the monosubstituted derivatives have been used to predict the shifts of each of the 1- and 3-methyl-2-norbornanols. The agreement between observed and calculated values is generally good and supports the general approach. Several ^(13)C-^(13)C coupling constants for norbornane, nortricyclene, and quadricyclene are reported and interpreted in terms of the s character of the C-C bonds.


Item Type:Article
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http://dx.doi.org/10.1021/ja00727a016DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja00727a016PublisherArticle
Additional Information:© 1970 American Chemical Society. Received February 28, 1970. Supported by the National Science Foundation.
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Caltech Gates and Crellin Laboratories of Chemistry3946
Issue or Number:24
Record Number:CaltechAUTHORS:20151012-133440486
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20151012-133440486
Official Citation:Nuclear magnetic resonance spectroscopy. Carbon-13 chemical shifts in norbornyl derivatives John D. Roberts, John B. Grutzner, Manfred Jautelat, Joseph B. Dence, and Robert A. Smith Journal of the American Chemical Society 1970 92 (24), 7107-7120 DOI: 10.1021/ja00727a016
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:60999
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:15 Oct 2015 03:46
Last Modified:03 Oct 2019 09:03

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