Fate of the intermediate diradicals in the caldera: Stereochemistry of thermal stereomutations, (2 + 2) cycloreversions, and (2 + 4) ring-enlargements of cis- and trans-1-cyano-2-(E and Z)-propenyl-cis-3,4-dideuteriocyclobutanes

Journal of the American Chemical Society

Volumn 124, Issue 39, 2002, Pages 11642-11652

  Doering, W von E ^a   Cheng, Xueheng ^a   Lee, Kyuwang ^a   Lin, Zisen ^a  

^a HARVARD UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

DIRADICALS;

CHEMICAL BONDS; CONFORMATIONS; ISOMERS; ORGANIC COMPOUNDS;

STEREOCHEMISTRY;

CYCLOBUTANE DERIVATIVE;

ARTICLE; CHEMICAL ANALYSIS; CHEMICAL MODIFICATION; CHEMICAL STRUCTURE; CIS TRANS ISOMERISM; STEREOCHEMISTRY; STEREOISOMERISM;

CYCLOBUTANES; DEUTERIUM; FREE RADICALS; HEATING; KINETICS; MAGNETIC RESONANCE SPECTROSCOPY; MOLECULAR CONFORMATION; STEREOISOMERISM;

EID: 0037010023     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0206083     Document Type: Article

References (49)

1. Lin, M. C.; Laidler, K. J. Trans. Faraday Soc. 1968, 64, 927-944, and cited references.
2. Doubleday, C., Jr. J. Phys. Chem. 1996, 100, 15083-15086, and cited references.
3. (a) Gerberich, H. R.; Walters, W. D. J. Am. Chem. Soc. 1961, 83, 3935-3939; 4884-4888.
4. (b) Chikos, J. S. J. Org. Chem. 1979, 44, 780-784. Chikos, J. S.; Annamalai, A.; Keiderling, T. A. J. Am. Chem. Soc. 1986, 108, 4398-4402.
5. (b) Chikos, J. S. J. Org. Chem. 1979, 44, 780-784. Chikos, J. S.; Annamalai, A.; Keiderling, T. A. J. Am. Chem. Soc. 1986, 108, 4398-4402.
6. (c) Goldstein, M. J.; Cannarsa, M. J.; Kinoshita, T.; Koniz, R. F. Stud. Org. Chem. (Amsterdam) 1987, 31, 121-133. Cannarsa, M. J. Ph.D. Dissertation, Cornell University, 1984; Diss. Abstr. Int. B 1984, 45, 1468 (Order No. 84-15,310).
7. (c) Goldstein, M. J.; Cannarsa, M. J.; Kinoshita, T.; Koniz, R. F. Stud. Org. Chem. (Amsterdam) 1987, 31, 121-133. Cannarsa, M. J. Ph.D. Dissertation, Cornell University, 1984; Diss. Abstr. Int. B 1984, 45, 1468 (Order No. 84-15,310).
8. (c) Goldstein, M. J.; Cannarsa, M. J.; Kinoshita, T.; Koniz, R. F. Stud. Org. Chem. (Amsterdam) 1987, 31, 121-133. Cannarsa, M. J. Ph.D. Dissertation, Cornell University, 1984; Diss. Abstr. Int. B 1984, 45, 1468 (Order No. 84-15,310).
9. (d) Berson, J. A.; Tomkins, D. C.; Jones, G., II. J. Am. Chem. Soc. 1970, 92, 5799-5800. Jones, G., II; Fantina, M. F. J. Chem. Soc., Chem. Commun. 1973, 375-377. Jones, G., II; Chow, V. L. J. Org. Chem. 1974, 39, 1447-1448.
10. (d) Berson, J. A.; Tomkins, D. C.; Jones, G., II. J. Am. Chem. Soc. 1970, 92, 5799-5800. Jones, G., II; Fantina, M. F. J. Chem. Soc., Chem. Commun. 1973, 375-377. Jones, G., II; Chow, V. L. J. Org. Chem. 1974, 39, 1447-1448.
11. (d) Berson, J. A.; Tomkins, D. C.; Jones, G., II. J. Am. Chem. Soc. 1970, 92, 5799-5800. Jones, G., II; Fantina, M. F. J. Chem. Soc., Chem. Commun. 1973, 375-377. Jones, G., II; Chow, V. L. J. Org. Chem. 1974, 39, 1447-1448.
12. (e) Doering, W. v. E.; Guyton, C. A. J. Am. Chem. Soc. 1978, 100, 3229-3230. Guyton, C. A. Ph.D. Dissertation, Harvard University, 1980; Diss. Abstr. Int. B 1980, 41, 1370.
13. (e) Doering, W. v. E.; Guyton, C. A. J. Am. Chem. Soc. 1978, 100, 3229-3230. Guyton, C. A. Ph.D. Dissertation, Harvard University, 1980; Diss. Abstr. Int. B 1980, 41, 1370.
14. (e) Doering, W. v. E.; Guyton, C. A. J. Am. Chem. Soc. 1978, 100, 3229-3230. Guyton, C. A. Ph.D. Dissertation, Harvard University, 1980; Diss. Abstr. Int. B 1980, 41, 1370.
15. (f) Hammond, G. S.; DeBoer, C. D. J. Am. Chem. Soc. 1964, 86, 899-905.
16. (g) Berson, J. A.; Dervan, P. B. J. Am. Chem. Soc. 1973, 95, 267-271; 1976, 98, 5937-5968.
17. (g) Berson, J. A.; Dervan, P. B. J. Am. Chem. Soc. 1973, 95, 267-271; 1976, 98, 5937-5968.
18. (g) Jordan, L. M. Ph.D. Dissertation, Yale University, 1974; Diss. Abstr. Int. B 1975, 35, 5332-5333.
19. (g) Jordan, L. M. Ph.D. Dissertation, Yale University, 1974; Diss. Abstr. Int. B 1975, 35, 5332-5333.
20. (h) Baldwin, J. E.; Burrell, R. C. J. Am. Chem. Soc. 2001, 123, 6718-6719.
21. Of the several advantages offered by the cyano group-acidifying effect, LIS-friendliness-not the least is its low steric value: Vögtle, F.; Neumann, P.; Zuber, M. Chem. Ber. 1972, 105, 2955-2962.
22. Doering, W. v. E.; Sachdev, K. J. Am. Chem. Soc. 1974, 96, 1168-1187; 1975, 97, 5512-5520.
23. Doering, W. v. E.; Sachdev, K. J. Am. Chem. Soc. 1974, 96, 1168-1187; 1975, 97, 5512-5520.
24. Doering, W. v. E.; Mastrocola, A. R. Tetrahedron 1981, 37, Suppl. 1, 329-344.
25. See for example: Srinivasan, R.; Hsu, J. C. N. J. Chem. Soc., Chem. Commun. 1972, 1213-1214. Wang, Y.-s.; Chickos, J. S. J. Org. Chem. 1987, 52, 4776-4781.
26. See for example: Srinivasan, R.; Hsu, J. C. N. J. Chem. Soc., Chem. Commun. 1972, 1213-1214. Wang, Y.-s.; Chickos, J. S. J. Org. Chem. 1987, 52, 4776-4781.
27. Doering, W. v. E.; Yamashita, Y. J. Am. Chem. Soc. 1983, 105, 5368-5372.
28. Tris(1,1,1,2,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octadionato)europium.
29. (a) Willcott, M. R., III; Lenkinski, R. E.; Davis, R. E. J. Am, Chem. Soc. 1972, 94, 1742-1744.
30. (b) Davis, R. E.; Willcott, M. R., III. J. Am. Chem. Soc. 1972, 94, 1744-1745.
31. (c) Doering, W. v. E.; Birladeanu, L. Tetrahedron 1973, 29, 499-512.
32. (d) Davis, R. E.; Willcott, M. R., III; Lenkinski, R. E.; Doering, W. v. E.; Birladeanu, L. J. Am. Chem. Soc. 1973, 95, 6846-6848.
33. (a) Raber, D. J.; Johnston, M. D., Jr.; Schwalke, M. A. J. Am. Chem. Soc. 1977, 99, 7671-7673.
34. (b) Raber, D. J.; Johnston, M. D., Jr.; Perry, J. W.; Jackson, G. F., III. J. Org. Chem. 1978, 43, 229-231.
35. (c) Raber, D. J.; Janks, C. M.; Johnston, M. D., Jr.; Raber, N. K. Org. Magn. Reson. 1981, 15, 57-76.
36. Seux, R.; Morel, G.; Foucand, A. Tetrahedron Lett. 1972, 1003-1006.
37. For a successful application to conformational equilibria in some acyclic nitriles, see ref 12a; and in cyanocyclohexane, ref 15.
38. Cheng, X.-h. Ph.D. Dissertation, Harvard University, 1988; Diss. Abstr. Int. B 1990, 50, 3472.
39. Cheng, X.-h. Ph.D. Dissertation, Harvard University, 1988; Diss. Abstr. Int. B 1990, 50, 3472.
40. Heats of formation of 3, 4, cyclobutane, and 3-methylcyclohexene are taken from Pedley, Naylor, and Kirby. Replacement of hydrogen by cyano is estimated following ref 16 in Doering and Wang.
41. Pedley, J. B.; Naylor, R. D.; Kirby, S. P. Thermochemical Data of Organic Compounds, 2nd ed; Chapman and Hall: London, 1986.
42. Doering, W. v. E.; Wang, Y.-h. J. Am. Chem. Soc. 1999, 121, 10967-10975.
43. Korth, H.-G.; Trill, H.; Sustmann, R. J. Am. Chem. Soc. 1981, 103, 4483-4489.
44. The small amount of material questionably suggested to be 5ee from 1ee in Table 3 is supported by GC retention time only.
45. In connection with synclinal (gauche), (-) and (+) designate helicity about the back, C-3-C-4, bond.
46. Doering, W. v. E.; Sachdev, K. J. Am. Chem. Soc. 1974, 96, 1168-1187.
47. Allinger, N. L. J. Am. Chem. Soc. 1977, 99, 8127-8132 (As made available in Cambridge Chem 3D plus 6.0).
48. Barsa, E. A. Ph.D. Dissertation, Harvard University. 1976; Diss. Abstr. Int. B 1977, 37, 5077 (pp 99-132).
49. Barsa, E. A. Ph.D. Dissertation, Harvard University. 1976; Diss. Abstr. Int. B 1977, 37, 5077 (pp 99-132).