Macromolecular Stereochemistry: A Cooperative Deuterium Isotope Effect Leading to a Large Optical Rotation

Journal of the American Chemical Society

Volumn 110, Issue 12, 1988, Pages 4063-4065

  Green, Mark M ^a   Andreola, Christopher ^a   Muñoz, Beth ^a   Reidy, Michael P ^a   Zero, Karl ^b  

^a POLYTECHNIC UNIVERSITY   (United States)

^b HONEYWELL   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 33845280516     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00220a070     Document Type: Article

References (18)

1. Prepared from (R)-1-deuterio-n-hexyl isocyanate (see ref 2 below) by anionic polymerization following: Shashoua, V. E.; Sweeny, W.; Tietz, R. F. J. Am. Chem. Soc. 1960, 82, 866.
2. 13C NMR specified the isotopic site at C-1. The isocyanate was prepared following: Farlow, M. W. Organic Syntheses; Wiley: New York, 1963; Collect. Vol. IV, p 521.
3. For early literature in the area of optically active isotopically substituted molecules, see: Loewus, F. A.; Westheimer, F. H.; Vennesland, B. J. Am. Chem. Soc. 1953, 75, 5018. Streitwieser, A., Jr. J. Am. Chem. Soc. 1953, 75, 5014. Levy, H. R.; Loewus, F. A.; Vennesland, B. J. Am. Chem. Soc. 1957, 79, 2949. Althouse, V. E.; Feigl, D. M.; Sanderson, W. A.; Mosher, H. S. J. Am. Chem. Soc. 1966, 88, 3595. For reviews, see: Arigoni, D.; Eliel, E. L. In Topics in Stereochemistry; Wiley: 1969; Vol. 4, p 127ff. Verbit, L. In Progress in Physical Organic Chemistry; Wiley-Interscience: 1970; Vol. 7, p 51ff; Barth, G.; Djerassi, C. Tetrahedron 1981, 37, 4123.
4. Troxell, T. C.; Scheraga, H. A. Macromolecules 1971, 4, 528. Milstein, J. B.; Charney, E. Macromolecules 1969, 2, 678.
5. 3 was 540 Å.
6. Goodman, M.; Chen, S. Macromolecules 1970, 3, 398
7. Green, M. M.; Gross, R. A.; Cook, R.; Schilling, F. C. Macromolecules 1987, 20, 2636. Green, M. M.; Gross, R. A.; Crosby, III, C.; Schilling, F. C. Macromolecules 1987, 20, 992.
8. A critical review is as follows: Bur, A.; Fetters, L. J. Chem. Rev. 1976, 76, 727. See, also: Berger, M. N.; Tidswell, B. M. J. Polym. Sci. Polym. Symp. 1973, No. 42, 1063.
9. See: Morawetz, H. Macromolecules in Solution; 2nd ed.; WileyInterscience: New York, 1975; p 242ff. Selegny (Optically Active Polymers; Selegny, E., Ed.; Reidel: Boston, 1979) gives many examples of this phenomenon in vinyl polymers. See especially the article by Selegny and Merle-Aubry (Selegny, E.; Merle-Aubry, L. p 15ff). Farina, M. In Topics in Stereochemistry; Eliel, E. L., Wilen, S. H., Eds.; 1987; Vol. 17, pp 1ff, 77, and 78, and references therein in particular.
10. For a general discussion of the circular dichroism characteristics of polymers, see: Sears, D. W.; Beychok, S. Physical Properties and Techniques of Protein Chemistry; Leach, S. J., Ed.; Academic Press: New York, 1973; Chapter 23, Part C, p 446ff. Tinoco, I., Jr. In Optically Active Polymers; Selegny, E., Ed.; Reidel: Boston, 1979; pp 1–13. See, also: Circular Dichroic Spectroscopy, Exciton Coupling in Organic Stereochemistry; Harada, N., Nakanishi, K., Eds.; University Science Books: Mill Valley, CA, 1983; references to Chapter 1 therein.
11. Thermal dependence of electronic spectral characteristics are also found in other conjugated polymers. See: Miller, R. D.; Hofer, D.; Rabolt, J.; Fickes, G. N. J. Am. Chem. Soc. 1985, 107, 2172. Miller, R. D.; Farmer, B. L.; Fleming, W.; Sooriyakumaran, R.; Rabolt, J. J. Am. Chem. Soc. 1987, 109, 2509.
12. For a recent paper in this area and leading references, see: Green, M. M.; Boyle, B. A.; Vairamani, M.; Mukhopadhyay, T.; Saunders, W. H., Jr.; Bowen, P.; Allinger, N. L. J. Am. Chem. Soc. 1986, 108, 2381.
13. Anet, F. A. L.; Kopelevich, M. J. Am. Chem. Soc. 1986, 108, 1355, 2109. Anet, F. A. L.; Kopelevich, M. J. Chem. Soc., Chem. Commun. 1987, 595. Servis, K. L.; Domenick, R. L.; Forsyth, D. A.; Pan, Yi. J. Am. Chem. Soc. 1987, 109, 7263. Forsyth, D. A.; Botkin, J. H.; Puckace, J. S.; Servis, K. L.; Domenick, R. L. J. Am. Chem. Soc. 1987, 109, 7270. Forsyth, D. A.; Hanley, J. A. J. Am. Chem. Soc. 1987, 109, 7930. For a review of the earlier literature, see: Melander, L.; Saunders, W. H., Jr. Reaction Rates of Isotopic Molecules; Wiley-Interscience: New York, 1980; pp 189–201.
14. Shmueli, K.; Traub, W.; Rosenheck, K. J. Polym. Sci. Part A-2 1969, 7, 515.
15. See ref 5 above and Tonelli (Tonelli, A. Macromolecules 1974, 7, 628).
16. Molecular Motion in High Polymers, Bailey, R. T., North, A. M., Pethrick, R. A., Eds.; Clarendon Press: Oxford, 1981; pp 67 and 203 and references therein.
17. See ref 5, 9, and 17 above and the following: Cook, R. Macromolecules 1987, 20, 1961. Bur, A. J.; Roberts, D. E. J. Chem. Phys. 1969, 51, 406.
18. Professor S. Lifson of the Weizmann Institute has completed a statistical mechanical analysis (to be published) which is consistent with the cooperative effect proposed here and makes predictions of the relationship between the energy difference per deuterium favoring one helical sense and the temperature dependence of the optical rotation. He has also made the challenging suggestion that the energy difference per residue in 1 could arise, at least in part, from an electrostatic interaction between the dipole of the C-H(D) bond αto nitrogen and one of the carbonyl oxygens. In such an interaction which could be described as a C-H to oxygen hydrogen bond, deuterium will differ, however slightly, from hydrogen. See: Melander and Saunders in ref 15 above, pp 197–198. Katz, J. J.; Crespi, H. L. In Isotope Effects in Chemical Reactions; ACS Monograph 167; Van Nostrand Reinhold: New York, 1970; Chapter 5. This idea could find support in the following: Taylor, R.; Kennard, O. J. Am. Chem. Soc. 1982, 104, 5063 and references therein. See, also: Seiler, P.; Weisman, G. R.; Glendening, E. D.; Weinhold, F.; Johnson, V.B.; Dunitz, J. D. Angew. Chem., Int. Ed. Engl. 1987, 26, 1175.