Effect of Ortho Substituants on the Direction of 1,2-Migrations in the Rearrangement of 2-exo-Arylfenchyl Alcohols

Journal of Organic Chemistry

Volumn 63, Issue 7, 1998, Pages 2262-2272

  Starling, Scott M ^a   Vonwiller, Simone C ^a   Reek, Joost N H ^a  

^a UNIVERSITY OF SYDNEY   (Australia)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000365688     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo972025v     Document Type: Article

References (45)

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3. Huang, E.; Ranganayakulu, K.; Sorensen, T. S. J. Am. Chem. Soc. 1972, 94, 1779. Sorensen, T. S. Acc. Chem. Res. 1976, 9, 257.
4. For example, see: Yuasa, Y.; Watanabe, T.; Nagakura, A.; Tsuruta, H. King, G. A. III; Sweeny, J. G.; Iacobucci, G. A. Tetrahedron 1992, 48, 3473.
5. Brown, H. C.; Takeuchi, K. J. Am. Chem. Soc. 1968, 90, 2693. arnum, D. G.; Mehta, G. J. Am. Chem. Soc. 1969, 91, 3256. Brown, H. C.; Takeuchi, K.; Ravindranathan, M. J. Am. Chem. Soc. 1977, 99, 2684. Substitution by electron-withdrawing groups increases the tendency toward nonclassical stabilization: Farnum, D. G.; Wolf, A. D. J. Am. Chem. Soc. 1974, 96, 5166.
6. Brown, H. C.; Takeuchi, K. J. Am. Chem. Soc. 1968, 90, 2693. arnum, D. G.; Mehta, G. J. Am. Chem. Soc. 1969, 91, 3256. Brown, H. C.; Takeuchi, K.; Ravindranathan, M. J. Am. Chem. Soc. 1977, 99, 2684. Substitution by electron-withdrawing groups increases the tendency toward nonclassical stabilization: Farnum, D. G.; Wolf, A. D. J. Am. Chem. Soc. 1974, 96, 5166.
7. Brown, H. C.; Takeuchi, K. J. Am. Chem. Soc. 1968, 90, 2693. arnum, D. G.; Mehta, G. J. Am. Chem. Soc. 1969, 91, 3256. Brown, H. C.; Takeuchi, K.; Ravindranathan, M. J. Am. Chem. Soc. 1977, 99, 2684. Substitution by electron-withdrawing groups increases the tendency toward nonclassical stabilization: Farnum, D. G.; Wolf, A. D. J. Am. Chem. Soc. 1974, 96, 5166.
8. Brown, H. C.; Takeuchi, K. J. Am. Chem. Soc. 1968, 90, 2693. arnum, D. G.; Mehta, G. J. Am. Chem. Soc. 1969, 91, 3256. Brown, H. C.; Takeuchi, K.; Ravindranathan, M. J. Am. Chem. Soc. 1977, 99, 2684. Substitution by electron-withdrawing groups increases the tendency toward nonclassical stabilization: Farnum, D. G.; Wolf, A. D. J. Am. Chem. Soc. 1974, 96, 5166.
9. For preliminary results see; (a) Starling, S. M.; Vonwiller, S. C. Tetrahedron Lett. 1997, 38, 2159. (b) Starling, S. M. Ph.D. Thesis, University of Sydney, 1997.
10. For preliminary results see; (a) Starling, S. M.; Vonwiller, S. C. Tetrahedron Lett. 1997, 38, 2159. (b) Starling, S. M. Ph.D. Thesis, University of Sydney, 1997.
11. Schleyer, P. v. R.; Lam, L. K. M.; Raber, D. J.; Fry, J. L.; McKervey, M. A.; Alford, J. R.; Cuddy, B. D.; Keizer, V. G.; Geluk, H. W.; Schlatmann, J. L. M. A. J. Am. Chem. Soc. 1970, 92, 5246. Majerski, Z.; Schleyer, P. v. R.; Wolf, A. P. J. Am. Chem. Soc. 1970, 92, 5731. Nickon, A.; Weglein, R. C. J. Am. Chem. Soc. 1975, 97, 1271. Paquette, L. A.; Waykole, L.; Jendralla, H.; Cottrell, C. E. J. Am. Chem. Soc. 1986, 108, 3739. Paquette, L. A.; Lanter, J. C.; Johnston, J. N. J. Org. Chem. 1997, 62, 1702.
12. Schleyer, P. v. R.; Lam, L. K. M.; Raber, D. J.; Fry, J. L.; McKervey, M. A.; Alford, J. R.; Cuddy, B. D.; Keizer, V. G.; Geluk, H. W.; Schlatmann, J. L. M. A. J. Am. Chem. Soc. 1970, 92, 5246. Majerski, Z.; Schleyer, P. v. R.; Wolf, A. P. J. Am. Chem. Soc. 1970, 92, 5731. Nickon, A.; Weglein, R. C. J. Am. Chem. Soc. 1975, 97, 1271. Paquette, L. A.; Waykole, L.; Jendralla, H.; Cottrell, C. E. J. Am. Chem. Soc. 1986, 108, 3739. Paquette, L. A.; Lanter, J. C.; Johnston, J. N. J. Org. Chem. 1997, 62, 1702.
13. Schleyer, P. v. R.; Lam, L. K. M.; Raber, D. J.; Fry, J. L.; McKervey, M. A.; Alford, J. R.; Cuddy, B. D.; Keizer, V. G.; Geluk, H. W.; Schlatmann, J. L. M. A. J. Am. Chem. Soc. 1970, 92, 5246. Majerski, Z.; Schleyer, P. v. R.; Wolf, A. P. J. Am. Chem. Soc. 1970, 92, 5731. Nickon, A.; Weglein, R. C. J. Am. Chem. Soc. 1975, 97, 1271. Paquette, L. A.; Waykole, L.; Jendralla, H.; Cottrell, C. E. J. Am. Chem. Soc. 1986, 108, 3739. Paquette, L. A.; Lanter, J. C.; Johnston, J. N. J. Org. Chem. 1997, 62, 1702.
14. Schleyer, P. v. R.; Lam, L. K. M.; Raber, D. J.; Fry, J. L.; McKervey, M. A.; Alford, J. R.; Cuddy, B. D.; Keizer, V. G.; Geluk, H. W.; Schlatmann, J. L. M. A. J. Am. Chem. Soc. 1970, 92, 5246. Majerski, Z.; Schleyer, P. v. R.; Wolf, A. P. J. Am. Chem. Soc. 1970, 92, 5731. Nickon, A.; Weglein, R. C. J. Am. Chem. Soc. 1975, 97, 1271. Paquette, L. A.; Waykole, L.; Jendralla, H.; Cottrell, C. E. J. Am. Chem. Soc. 1986, 108, 3739. Paquette, L. A.; Lanter, J. C.; Johnston, J. N. J. Org. Chem. 1997, 62, 1702.
15. Schleyer, P. v. R.; Lam, L. K. M.; Raber, D. J.; Fry, J. L.; McKervey, M. A.; Alford, J. R.; Cuddy, B. D.; Keizer, V. G.; Geluk, H. W.; Schlatmann, J. L. M. A. J. Am. Chem. Soc. 1970, 92, 5246. Majerski, Z.; Schleyer, P. v. R.; Wolf, A. P. J. Am. Chem. Soc. 1970, 92, 5731. Nickon, A.; Weglein, R. C. J. Am. Chem. Soc. 1975, 97, 1271. Paquette, L. A.; Waykole, L.; Jendralla, H.; Cottrell, C. E. J. Am. Chem. Soc. 1986, 108, 3739. Paquette, L. A.; Lanter, J. C.; Johnston, J. N. J. Org. Chem. 1997, 62, 1702.
16. Smith, A. B., III; Wexler, B. A.; Tu, C.-Y.; Konopelski, J. P. J. Am. Chem. Soc. 1985, 107, 1308.
17. See also: Kočovský, P.; Turecek, F.; Langer, V.; Podhlahová, J.; Podlaha, J. J. Org. Chem. 1986, 51, 4888.
18. 3 to nucleophilic attack by aryllithium reagents (see ref 10) is not supported by our results.
19. 11c (1R,2R,4S)-Enantiomer: Genov, M.; Kostova, K.; Dimitrov, V. Tetrahedron: Asymmetry 1997, 8, 1869.
20. Our initial assignment of the precursor to the hexahydroazafluorene was incorrect: ref 5a.
21. The formation of cyclofenchenes and related compounds is relatively well-known in aprotic solvents: Bartlett, P. D.; Webster, E. R.; Dills, C. E.; Richey, H. G., Jr. Justus Liebigs Ann. Chem. 1959, 623, 217; Ref: 13.
22. Fry, J. L.; West, J. W. J. Org. Chem. 1981, 46, 2177.
23. 2 group and have a destabilizing effect on carbocation formation. However, under aqueous conditions, the pKa's of protonated anilines are actually lower than those for carboxylic acids; see: March, J. Advanced Organic Chemistry; John Wiley & Sons: New York, 1992; p 251. Reichardt, C. Solvent Effects in Organic Chemistry; VCH: Weinheim, 1990; pp 89-91. Arnett, E. M. J. Chem. Educ. 1985, 62, 385. Thus, there will be an equilibrium mixture of the unprotonated, monoprotonated, and diprotonated hydroxy anilines, and it is expected that species i will be the only one significant for carbocation formation and subsequent rearrangement. The effect of protonation therefore is simply to decrease the rate of carbocation formation.
24. 2 group and have a destabilizing effect on carbocation formation. However, under aqueous conditions, the pKa's of protonated anilines are actually lower than those for carboxylic acids; see: March, J. Advanced Organic Chemistry; John Wiley & Sons: New York, 1992; p 251. Reichardt, C. Solvent Effects in Organic Chemistry; VCH: Weinheim, 1990; pp 89-91. Arnett, E. M. J. Chem. Educ. 1985, 62, 385. Thus, there will be an equilibrium mixture of the unprotonated, monoprotonated, and diprotonated hydroxy anilines, and it is expected that species i will be the only one significant for carbocation formation and subsequent rearrangement. The effect of protonation therefore is simply to decrease the rate of carbocation formation.
25. 2 group and have a destabilizing effect on carbocation formation. However, under aqueous conditions, the pKa's of protonated anilines are actually lower than those for carboxylic acids; see: March, J. Advanced Organic Chemistry; John Wiley & Sons: New York, 1992; p 251. Reichardt, C. Solvent Effects in Organic Chemistry; VCH: Weinheim, 1990; pp 89-91. Arnett, E. M. J. Chem. Educ. 1985, 62, 385. Thus, there will be an equilibrium mixture of the unprotonated, monoprotonated, and diprotonated hydroxy anilines, and it is expected that species i will be the only one significant for carbocation formation and subsequent rearrangement. The effect of protonation therefore is simply to decrease the rate of carbocation formation. Equation presented.
26. (15) Compounds 4b and 4c are of interest because of their structural relationship to the cannabinoids. 4c can be considered as an analogue of cannabielsoin although the latter shows no CNS activity: Uliss, D. B.; Razdan, R. K.; Dalzell. H. C. J. Am. Chem. Soc. 1974, 96, 7372.
27. The reported NMR data are consistent with our data for the Nametkin product (see Experimental Section).
28. For X-ray crystallographic data supporting the tendency for exo-methyl migration in the Nametkin rearrangement, see: Moews, P. C.; Knox, J. R.; Vaughan, W. R. J. Am. Chem. Soc. 1978, 100, 260. Cameron, T. S.; Jochem, K.; Morris, D. G.; Maguire, J. Acta Crystallogr. 1994, C50, 2085.
29. For X-ray crystallographic data supporting the tendency for exo-methyl migration in the Nametkin rearrangement, see: Moews, P. C.; Knox, J. R.; Vaughan, W. R. J. Am. Chem. Soc. 1978, 100, 260. Cameron, T. S.; Jochem, K.; Morris, D. G.; Maguire, J. Acta Crystallogr. 1994, C50, 2085.
30. Brouwer, D. M.; Hogeveen, H. Red. Trav. Chim. Pays-Bas 1970, 89, 211.
31. Heagy, M. D.; Olah, G. A.; Prakash, G. K. S. J. Org. Chem. 1995, 60, 7355.
32. Carey, F. A.; Sundberg, R. J. Advanced Organic Chemistry Part A: Structure and Mechanisms, Plenum Press: New York, 1990; p 201.
33. Page, M. I. Chem. Soc. Rev. 1973, 2, 295.
34. Oxygen donor groups: Paquette, L. A.; Scott, M. K. J. Am. Chem. Soc. 1972, 94, 6760. Gassman, P. G.; Marshall, J. L.; Macmillan: J. G. J. Am. Chem. Soc. 1973, 95, 6319, Eliel, E. L.; Clawson, L.; Knox, D. E. J. Org. Chem. 1985, 50, 2707. Sulfur donor groups: Eliel, E. L.; Knox, D. E. J. Am. Chem. Soc. 1985, 107, 2946.
35. Oxygen donor groups: Paquette, L. A.; Scott, M. K. J. Am. Chem. Soc. 1972, 94, 6760. Gassman, P. G.; Marshall, J. L.; Macmillan: J. G. J. Am. Chem. Soc. 1973, 95, 6319, Eliel, E. L.; Clawson, L.; Knox, D. E. J. Org. Chem. 1985, 50, 2707. Sulfur donor groups: Eliel, E. L.; Knox, D. E. J. Am. Chem. Soc. 1985, 107, 2946.
36. Oxygen donor groups: Paquette, L. A.; Scott, M. K. J. Am. Chem. Soc. 1972, 94, 6760. Gassman, P. G.; Marshall, J. L.; Macmillan: J. G. J. Am. Chem. Soc. 1973, 95, 6319, Eliel, E. L.; Clawson, L.; Knox, D. E. J. Org. Chem. 1985, 50, 2707. Sulfur donor groups: Eliel, E. L.; Knox, D. E. J. Am. Chem. Soc. 1985, 107, 2946.
37. Oxygen donor groups: Paquette, L. A.; Scott, M. K. J. Am. Chem. Soc. 1972, 94, 6760. Gassman, P. G.; Marshall, J. L.; Macmillan: J. G. J. Am. Chem. Soc. 1973, 95, 6319, Eliel, E. L.; Clawson, L.; Knox, D. E. J. Org. Chem. 1985, 50, 2707. Sulfur donor groups: Eliel, E. L.; Knox, D. E. J. Am. Chem. Soc. 1985, 107, 2946.
38. Winstein, S.; Trifan, D. S. J. Am. Chem. Soc. 1949, 71, 2953.
39. For other relevant examples of apparently anchimerically assisted Wagner-Meerwein rearrangements, see: (a) McCapra, F.; Beheshti, I. J. Chem. Soc., Chem. Commun. 1977, 517. (b) Kondratenko, M.; El Hafa, H.; Gruselle, M.; Vaissermann, J.; Jaouen, G.; McGlinchey, M. J. J. Am. Chem. Soc. 1995, 117, 6907.
40. For other relevant examples of apparently anchimerically assisted Wagner-Meerwein rearrangements, see: (a) McCapra, F.; Beheshti, I. J. Chem. Soc., Chem. Commun. 1977, 517. (b) Kondratenko, M.; El Hafa, H.; Gruselle, M.; Vaissermann, J.; Jaouen, G.; McGlinchey, M. J. J. Am. Chem. Soc. 1995, 117, 6907.
41. By TLC a faint spot of intermediate polarity is evident throughout the reactions and is likely to be the cyclofenchene, although this was never formed in amounts sufficient for isolation and characterization.
42. Perrin, D. D.; Armarego, W. L. F. K.; Perrin, D. R. Purification of Laboratory Chemicals; Pergamon: Oxford, 1980.
43. Winkle, M. R.; Lansinger, J. M.; Ronald, R. C. J. Chem. Soc., Chem. Commun. 1980, 87.
44. Kofron, W. G.; Baclawski, L. M. J. Org. Chem. 1976, 41, 1879.
45. SPARTAN 4.0, Wavefunction, Inc., 18401 Von Karman, Suite 370, Irvine, CA 92715.