Separation of Nuclear Magnetic Resonance Signals of Internally Enantiotropic Protons Using a Chiral Shift Reagent. The Deuterium Isotope Effect on Geminal Proton-Proton Coupling Constants

Journal of the American Chemical Society

Volumn 94, Issue 9, 1972, Pages 3253-3254

  Fraser, Robert R ^a   Petit, Michel A ^a   Miskow, Maurice ^a  

^a UNIVERSITY OF OTTAWA   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0038683815     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00764a070     Document Type: Letter

References (15)

1. G. M. Whitesides and D. W. Lewis, J. Amer. Chem. Soc., 92, 6979 (1970);
2. G. M. Whitesides and O. W. Lewis, J. Amer. Chem. Soc., 93, 5914 (1971);
3. H. L. Goering, J. N. Eikenberry, and G. S. Koermer, J. Amer. Chem. Soc., 93, 5913 (1971);
4. R. R. Fraser, M. Petit, and J. K. Saunders, Chem. Commun., 1450 (1971).
5. Recent evidence indicates that lanthanide-induced shifts are produced primarily by a pseudocontact mechanism; see J. K. M. Saunders and D. M. Williams, Tetrahedron Lett., 2812 (1971);
6. H. Huber and C. Pascal, Helv, Chim. Acta, 54, 913 (1971);
7. for a recent compilation of references on shift reagents see W. W. DeHorrocks, Jr., J. P. Sipe III, and J. R. Luber, J. Amer. Chem. Soc., 93, 5258 (1971).
8. M. Raban and K. Mislow, Top. Stereochem., 1, 1 (1967).
9. All geminal coupling constants discussed in this paper are assumed to be negative as has been established for other benzylic protons; see R. R. Fraser, Can. J. Chem., 40, 1483 (1962).
10. 2-Ph bond is the one in which the oxygen atom lies in or nearly in the plane of the benzene ring.
11. H-H(see J. A. Pople, W. G. Schneider, and H. J. Bernstein, “High-Resolution Nuclear Magnetic Resonance,” McGraw-Hill, New York, N. Y., 1959, p 188). This assumption neglects changes in electron distribution resulting from the isotopic substitution.
12. R. M. Moriarty, J. P. Kim, S. J. Druck, and E. Lustig, Tetrahedron, 25, 1261 (1969).
13. Ch. Brevard, J. P. Kintzinger, and J. M. Lehn, Chem. Commun., 1193 (1969).
14. T. Durst, R. Viau, and M. R. McClory, J. Amer. Chem. Soc., 93, 3077 (1971);
15. T. Durst, R. R. Fraser, M. R. McClory, R. B. Swingle, R. Viau, and Y. Y. Wigfield, Can. J. Chem., 48, 2148 (1970). We wish to thank Mr. Viau for samples of the deuterated sulfoxide.