An NMR strategy for determination of configuration of remote stereogenic centers: 3-methylcarboxylic acids

Journal of the American Chemical Society

Volumn 120, Issue 19, 1998, Pages 4638-4643

  Hoye, Thomas R ^a   Koltun, Dmitry O ^a  

^a University of Minnesota   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CARBOXYLIC ACID DERIVATIVE;

ARTICLE; CHEMICAL STRUCTURE; NUCLEAR MAGNETIC RESONANCE; STEREOCHEMISTRY; STRUCTURE ACTIVITY RELATION;

EID: 0032550683     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja972664n     Document Type: Article

References (29)

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2. (b) Parker, D. Chem. Rev. 1991, 91, 1441. It is important to distinguish between (the more numerous) methods that are suitable for determination of enantiomeric excess and those useful for the more demanding task of determination of configuration (e.g., Valentine, D., Jr.; Chan, K. K.; Scott, C. G.; Johnson, K. K.; Toth, K.; Saucy, G. J. Org. Chem. 1976, 41, 62).
3. (b) Parker, D. Chem. Rev. 1991, 91, 1441. It is important to distinguish between (the more numerous) methods that are suitable for determination of enantiomeric excess and those useful for the more demanding task of determination of configuration (e.g., Valentine, D., Jr.; Chan, K. K.; Scott, C. G.; Johnson, K. K.; Toth, K.; Saucy, G. J. Org. Chem. 1976, 41, 62).
4. Yasuhara, F.; Yamaguchi, S. Tetrahedron Lett. 1977, 4085 and subsequent applications of that method.
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13. It is interesting that there appears to be a stepwise rather than linear correlation between the rate of decease in the magnitude of the Δδ values and the number of methylenes in the isoamides. This suggests that an "even-odd" effect may be operative.
14. Comparison of magnitude and sign of Δδ values between analogous pairs of resonances in two diasteromeric derivatives is a commonly used NMR strategy for deducing configuration and is most frequently encountered in the Mosher method: (a) Dale, J. A.; Dull, D. L.; Mosher, H. S. J. Org. Chem. 1969, 34, 2543. (b) Dale, J. A.; Mosher, H. S. J. Am. Chem. Soc. 1973, 95, 512. (c) Sullivan, G. R.; Dale, J. A.; Mosher, H. S. J. Org. Chem. 1973, 38, 2143. (d) Ohtani, I.; Kusumi, T.; Kashman, Y.; Kakisawa, H. J. Am. Chem. Soc. 1991, 113, 4092.
15. Comparison of magnitude and sign of Δδ values between analogous pairs of resonances in two diasteromeric derivatives is a commonly used NMR strategy for deducing configuration and is most frequently encountered in the Mosher method: (a) Dale, J. A.; Dull, D. L.; Mosher, H. S. J. Org. Chem. 1969, 34, 2543. (b) Dale, J. A.; Mosher, H. S. J. Am. Chem. Soc. 1973, 95, 512. (c) Sullivan, G. R.; Dale, J. A.; Mosher, H. S. J. Org. Chem. 1973, 38, 2143. (d) Ohtani, I.; Kusumi, T.; Kashman, Y.; Kakisawa, H. J. Am. Chem. Soc. 1991, 113, 4092.
16. Comparison of magnitude and sign of Δδ values between analogous pairs of resonances in two diasteromeric derivatives is a commonly used NMR strategy for deducing configuration and is most frequently encountered in the Mosher method: (a) Dale, J. A.; Dull, D. L.; Mosher, H. S. J. Org. Chem. 1969, 34, 2543. (b) Dale, J. A.; Mosher, H. S. J. Am. Chem. Soc. 1973, 95, 512. (c) Sullivan, G. R.; Dale, J. A.; Mosher, H. S. J. Org. Chem. 1973, 38, 2143. (d) Ohtani, I.; Kusumi, T.; Kashman, Y.; Kakisawa, H. J. Am. Chem. Soc. 1991, 113, 4092.
17. Comparison of magnitude and sign of Δδ values between analogous pairs of resonances in two diasteromeric derivatives is a commonly used NMR strategy for deducing configuration and is most frequently encountered in the Mosher method: (a) Dale, J. A.; Dull, D. L.; Mosher, H. S. J. Org. Chem. 1969, 34, 2543. (b) Dale, J. A.; Mosher, H. S. J. Am. Chem. Soc. 1973, 95, 512. (c) Sullivan, G. R.; Dale, J. A.; Mosher, H. S. J. Org. Chem. 1973, 38, 2143. (d) Ohtani, I.; Kusumi, T.; Kashman, Y.; Kakisawa, H. J. Am. Chem. Soc. 1991, 113, 4092.
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19. 12b
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23. 1H NMR spectral data vis-à-vis those of the 10s/10a and 15s/15a pairs.
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29. The assignment of resonances to the methyl groups (6Z and 6E) for the 11s/11a and 16s/16a pairs is based both on their relative chemical shifts [cf. other 1,1-dimethyl-substituted alkenes in which the cis-methyl group appears upfield from the trans-methyl group (e.g., the six cis-disposed methyl groups in squalene have a chemical shift of 1.60 ppm while the two trans-disposed methyls are at 1.68 ppm)]. Even if the differential anisotropic shielding effect of the aromatic ring in either of these pairs were sufficiently large to reverse that assignment for one or both of the diastereomers, the signs of the resulting Δδ values would remain negative.