Effects of substituents in the 3-position on the [2 + 2] pentadienyl cation electrocyclization

Journal of Organic Chemistry

Volumn 62, Issue 15, 1997, Pages 5110-5115

  Smith, Douglas A ^a   Ulmer II, Charles W ^a  

^a DASGroup Inc   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

1,4 PENTADIENYL CATION; ALUMINUM; BORON; CATION; HYDROGEN; IMINE; OXYGEN; PHOSPHORUS; SULFUR; THIOKETONE; UNCLASSIFIED DRUG;

ARTICLE; CONFORMATION; CYCLIZATION; ENERGY; STEREOSPECIFICITY; SYNTHESIS;

EID: 0030807652     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo9703313     Document Type: Article

References (40)

1. Taken in part from the Ph.D. dissertation of CWU, The University of Toledo Department of Chemistry, 1995.
2. (a) Smith, D. A.; Ulmer, C. W., II. Tetrahedron Lett. 1991, 32, 725.
3. (b) Smith, D. A.; Ulmer, C. W., II. J. Org. Chem. 1991, 56, 4444.
4. (c) Smith, D. A.; Ulmer, C. W., II. J. Org. Chem. 1993, 58, 4118.
5. (d) Smith, D. A.; Ulmer, C. W., II. J. Mol. Graphics 1995, 13, 283.
6. Nazarov, I. N. Usp. Khim. 1949, 18, 377. Chem. Abstr. 1951, 45, 6572. Usp. Khim. 1951, 20, 71. Chem. Abstr. 1954, 48, 611. For reviews, see: Santelli-Rouvier, C.; Santelli, M. Synthesis 1983, 429; Habermas, K. L., Denmark, S. E.; Jones, T. K. The Nazarov Cyclization. in Organic Reactions; Paquette, L., Ed., 1994; Vol. 45.
7. Nazarov, I. N. Usp. Khim. 1949, 18, 377. Chem. Abstr. 1951, 45, 6572. Usp. Khim. 1951, 20, 71. Chem. Abstr. 1954, 48, 611. For reviews, see: Santelli-Rouvier, C.; Santelli, M. Synthesis 1983, 429; Habermas, K. L., Denmark, S. E.; Jones, T. K. The Nazarov Cyclization. in Organic Reactions; Paquette, L., Ed., 1994; Vol. 45.
8. Nazarov, I. N. Usp. Khim. 1949, 18, 377. Chem. Abstr. 1951, 45, 6572. Usp. Khim. 1951, 20, 71. Chem. Abstr. 1954, 48, 611. For reviews, see: Santelli-Rouvier, C.; Santelli, M. Synthesis 1983, 429; Habermas, K. L., Denmark, S. E.; Jones, T. K. The Nazarov Cyclization. in Organic Reactions; Paquette, L., Ed., 1994; Vol. 45.
9. Nazarov, I. N. Usp. Khim. 1949, 18, 377. Chem. Abstr. 1951, 45, 6572. Usp. Khim. 1951, 20, 71. Chem. Abstr. 1954, 48, 611. For reviews, see: Santelli-Rouvier, C.; Santelli, M. Synthesis 1983, 429; Habermas, K. L., Denmark, S. E.; Jones, T. K. The Nazarov Cyclization. in Organic Reactions; Paquette, L., Ed., 1994; Vol. 45.
10. Nazarov, I. N. Usp. Khim. 1949, 18, 377. Chem. Abstr. 1951, 45, 6572. Usp. Khim. 1951, 20, 71. Chem. Abstr. 1954, 48, 611. For reviews, see: Santelli-Rouvier, C.; Santelli, M. Synthesis 1983, 429; Habermas, K. L., Denmark, S. E.; Jones, T. K. The Nazarov Cyclization. in Organic Reactions; Paquette, L., Ed., 1994; Vol. 45.
11. Nazarov, I. N. Usp. Khim. 1949, 18, 377. Chem. Abstr. 1951, 45, 6572. Usp. Khim. 1951, 20, 71. Chem. Abstr. 1954, 48, 611. For reviews, see: Santelli-Rouvier, C.; Santelli, M. Synthesis 1983, 429; Habermas, K. L., Denmark, S. E.; Jones, T. K. The Nazarov Cyclization. in Organic Reactions; Paquette, L., Ed., 1994; Vol. 45.
12. For a sample of natural products containing the cyclopentane ring system, see; (a) Paquette, L. A. Top. Curr. Chem. 1984, 119, 1. (b) Bindra, J. S.; Bindra, R. Prostaglandin Synthesis; Academic Press: New York, 1977. (c) El-Naggar, L. J.; Beal, J. L. J. Nat. Prod. 1980, 46, 649. (d) Tietze L. F. Angew. Chem. 1983, 95, 840. (e) Heathcock, C. H.; Graham, S. L.; Pirrung, M. C.; Pavlac, F.; White, C. T. Total Synthesis of Natural Products; ApSimon, J., Ed.; Wiley: New York, 1983, Vol. 5, pp 333-381. (f) Vandewalle, M.; DeClerg, P. Tetrahedron 1985, 41, 1767. (g) Paquette, L. A.; Andres, D. R.; Springer, J. P. J. Org. Chem. 1983, 48, 1147. (h) Coates, R. M.; Senter, P. D.; Baker, W. R. Ibid. 1982, 47, 3597. (i) Harding, K. E.; Clement, K. S. Ibid. 1984, 49, 3870. (j) Crisp, G. T.; Scott, W. J.; Stille, J. K. J. Am. Chem. Soc. 1984, 106, 7500. For a sample of the synthesis of natural products using the Nazarov cyclization, see: (k) (±) - Trichodine: Harding, K. E.; Clement, K. S. J. Org. Chem. 1984, 49, 3870, (l) (±)-Modhephene: Schostarcz, H.; Paquette, L. A. Tetrahedron 1981, 37, 4431. (m) (±)-Stigol: MacAlpine, G. A.; Raphael, R. A.; Shaw, A.; Taylor, A.; Wild, H. J. J. Chem. Soc., Perkin Trans. 1 1976, 410. (n) (±)-Muscone: Baumann, M.; Hoffmann, W.; Muller, N. Tetrahedron Lett. 1976, 3583. (o) (±)-Nootkatone and (±)-muscopyridine: Hiyama, T.; Shinoda, M.; Saimoto, H.; Nozaki, H. Bull. Chem. Soc. Jpn. 1981, 54, 2747. (p) Diterpenoids and sesterterpenoids: Mehta, G.; Krishnamurthy, N. J. Chem. Soc., Chem. Commun. 1986, 1319.
13. For a sample of natural products containing the cyclopentane ring system, see; (a) Paquette, L. A. Top. Curr. Chem. 1984, 119, 1. (b) Bindra, J. S.; Bindra, R. Prostaglandin Synthesis; Academic Press: New York, 1977. (c) El-Naggar, L. J.; Beal, J. L. J. Nat. Prod. 1980, 46, 649. (d) Tietze L. F. Angew. Chem. 1983, 95, 840. (e) Heathcock, C. H.; Graham, S. L.; Pirrung, M. C.; Pavlac, F.; White, C. T. Total Synthesis of Natural Products; ApSimon, J., Ed.; Wiley: New York, 1983, Vol. 5, pp 333-381. (f) Vandewalle, M.; DeClerg, P. Tetrahedron 1985, 41, 1767. (g) Paquette, L. A.; Andres, D. R.; Springer, J. P. J. Org. Chem. 1983, 48, 1147. (h) Coates, R. M.; Senter, P. D.; Baker, W. R. Ibid. 1982, 47, 3597. (i) Harding, K. E.; Clement, K. S. Ibid. 1984, 49, 3870. (j) Crisp, G. T.; Scott, W. J.; Stille, J. K. J. Am. Chem. Soc. 1984, 106, 7500. For a sample of the synthesis of natural products using the Nazarov cyclization, see: (k) (±) - Trichodine: Harding, K. E.; Clement, K. S. J. Org. Chem. 1984, 49, 3870, (l) (±)-Modhephene: Schostarcz, H.; Paquette, L. A. Tetrahedron 1981, 37, 4431. (m) (±)-Stigol: MacAlpine, G. A.; Raphael, R. A.; Shaw, A.; Taylor, A.; Wild, H. J. J. Chem. Soc., Perkin Trans. 1 1976, 410. (n) (±)-Muscone: Baumann, M.; Hoffmann, W.; Muller, N. Tetrahedron Lett. 1976, 3583. (o) (±)-Nootkatone and (±)-muscopyridine: Hiyama, T.; Shinoda, M.; Saimoto, H.; Nozaki, H. Bull. Chem. Soc. Jpn. 1981, 54, 2747. (p) Diterpenoids and sesterterpenoids: Mehta, G.; Krishnamurthy, N. J. Chem. Soc., Chem. Commun. 1986, 1319.
14. For a sample of natural products containing the cyclopentane ring system, see; (a) Paquette, L. A. Top. Curr. Chem. 1984, 119, 1. (b) Bindra, J. S.; Bindra, R. Prostaglandin Synthesis; Academic Press: New York, 1977. (c) El-Naggar, L. J.; Beal, J. L. J. Nat. Prod. 1980, 46, 649. (d) Tietze L. F. Angew. Chem. 1983, 95, 840. (e) Heathcock, C. H.; Graham, S. L.; Pirrung, M. C.; Pavlac, F.; White, C. T. Total Synthesis of Natural Products; ApSimon, J., Ed.; Wiley: New York, 1983, Vol. 5, pp 333-381. (f) Vandewalle, M.; DeClerg, P. Tetrahedron 1985, 41, 1767. (g) Paquette, L. A.; Andres, D. R.; Springer, J. P. J. Org. Chem. 1983, 48, 1147. (h) Coates, R. M.; Senter, P. D.; Baker, W. R. Ibid. 1982, 47, 3597. (i) Harding, K. E.; Clement, K. S. Ibid. 1984, 49, 3870. (j) Crisp, G. T.; Scott, W. J.; Stille, J. K. J. Am. Chem. Soc. 1984, 106, 7500. For a sample of the synthesis of natural products using the Nazarov cyclization, see: (k) (±) - Trichodine: Harding, K. E.; Clement, K. S. J. Org. Chem. 1984, 49, 3870, (l) (±)-Modhephene: Schostarcz, H.; Paquette, L. A. Tetrahedron 1981, 37, 4431. (m) (±)-Stigol: MacAlpine, G. A.; Raphael, R. A.; Shaw, A.; Taylor, A.; Wild, H. J. J. Chem. Soc., Perkin Trans. 1 1976, 410. (n) (±)-Muscone: Baumann, M.; Hoffmann, W.; Muller, N. Tetrahedron Lett. 1976, 3583. (o) (±)-Nootkatone and (±)-muscopyridine: Hiyama, T.; Shinoda, M.; Saimoto, H.; Nozaki, H. Bull. Chem. Soc. Jpn. 1981, 54, 2747. (p) Diterpenoids and sesterterpenoids: Mehta, G.; Krishnamurthy, N. J. Chem. Soc., Chem. Commun. 1986, 1319.
15. For a sample of natural products containing the cyclopentane ring system, see; (a) Paquette, L. A. Top. Curr. Chem. 1984, 119, 1. (b) Bindra, J. S.; Bindra, R. Prostaglandin Synthesis; Academic Press: New York, 1977. (c) El-Naggar, L. J.; Beal, J. L. J. Nat. Prod. 1980, 46, 649. (d) Tietze L. F. Angew. Chem. 1983, 95, 840. (e) Heathcock, C. H.; Graham, S. L.; Pirrung, M. C.; Pavlac, F.; White, C. T. Total Synthesis of Natural Products; ApSimon, J., Ed.; Wiley: New York, 1983, Vol. 5, pp 333-381. (f) Vandewalle, M.; DeClerg, P. Tetrahedron 1985, 41, 1767. (g) Paquette, L. A.; Andres, D. R.; Springer, J. P. J. Org. Chem. 1983, 48, 1147. (h) Coates, R. M.; Senter, P. D.; Baker, W. R. Ibid. 1982, 47, 3597. (i) Harding, K. E.; Clement, K. S. Ibid. 1984, 49, 3870. (j) Crisp, G. T.; Scott, W. J.; Stille, J. K. J. Am. Chem. Soc. 1984, 106, 7500. For a sample of the synthesis of natural products using the Nazarov cyclization, see: (k) (±) - Trichodine: Harding, K. E.; Clement, K. S. J. Org. Chem. 1984, 49, 3870, (l) (±)-Modhephene: Schostarcz, H.; Paquette, L. A. Tetrahedron 1981, 37, 4431. (m) (±)-Stigol: MacAlpine, G. A.; Raphael, R. A.; Shaw, A.; Taylor, A.; Wild, H. J. J. Chem. Soc., Perkin Trans. 1 1976, 410. (n) (±)-Muscone: Baumann, M.; Hoffmann, W.; Muller, N. Tetrahedron Lett. 1976, 3583. (o) (±)-Nootkatone and (±)-muscopyridine: Hiyama, T.; Shinoda, M.; Saimoto, H.; Nozaki, H. Bull. Chem. Soc. Jpn. 1981, 54, 2747. (p) Diterpenoids and sesterterpenoids: Mehta, G.; Krishnamurthy, N. J. Chem. Soc., Chem. Commun. 1986, 1319.
16. For a sample of natural products containing the cyclopentane ring system, see; (a) Paquette, L. A. Top. Curr. Chem. 1984, 119, 1. (b) Bindra, J. S.; Bindra, R. Prostaglandin Synthesis; Academic Press: New York, 1977. (c) El-Naggar, L. J.; Beal, J. L. J. Nat. Prod. 1980, 46, 649. (d) Tietze L. F. Angew. Chem. 1983, 95, 840. (e) Heathcock, C. H.; Graham, S. L.; Pirrung, M. C.; Pavlac, F.; White, C. T. Total Synthesis of Natural Products; ApSimon, J., Ed.; Wiley: New York, 1983, Vol. 5, pp 333-381. (f) Vandewalle, M.; DeClerg, P. Tetrahedron 1985, 41, 1767. (g) Paquette, L. A.; Andres, D. R.; Springer, J. P. J. Org. Chem. 1983, 48, 1147. (h) Coates, R. M.; Senter, P. D.; Baker, W. R. Ibid. 1982, 47, 3597. (i) Harding, K. E.; Clement, K. S. Ibid. 1984, 49, 3870. (j) Crisp, G. T.; Scott, W. J.; Stille, J. K. J. Am. Chem. Soc. 1984, 106, 7500. For a sample of the synthesis of natural products using the Nazarov cyclization, see: (k) (±) - Trichodine: Harding, K. E.; Clement, K. S. J. Org. Chem. 1984, 49, 3870, (l) (±)-Modhephene: Schostarcz, H.; Paquette, L. A. Tetrahedron 1981, 37, 4431. (m) (±)-Stigol: MacAlpine, G. A.; Raphael, R. A.; Shaw, A.; Taylor, A.; Wild, H. J. J. Chem. Soc., Perkin Trans. 1 1976, 410. (n) (±)-Muscone: Baumann, M.; Hoffmann, W.; Muller, N. Tetrahedron Lett. 1976, 3583. (o) (±)-Nootkatone and (±)-muscopyridine: Hiyama, T.; Shinoda, M.; Saimoto, H.; Nozaki, H. Bull. Chem. Soc. Jpn. 1981, 54, 2747. (p) Diterpenoids and sesterterpenoids: Mehta, G.; Krishnamurthy, N. J. Chem. Soc., Chem. Commun. 1986, 1319.
17. For a sample of natural products containing the cyclopentane ring system, see; (a) Paquette, L. A. Top. Curr. Chem. 1984, 119, 1. (b) Bindra, J. S.; Bindra, R. Prostaglandin Synthesis; Academic Press: New York, 1977. (c) El-Naggar, L. J.; Beal, J. L. J. Nat. Prod. 1980, 46, 649. (d) Tietze L. F. Angew. Chem. 1983, 95, 840. (e) Heathcock, C. H.; Graham, S. L.; Pirrung, M. C.; Pavlac, F.; White, C. T. Total Synthesis of Natural Products; ApSimon, J., Ed.; Wiley: New York, 1983, Vol. 5, pp 333-381. (f) Vandewalle, M.; DeClerg, P. Tetrahedron 1985, 41, 1767. (g) Paquette, L. A.; Andres, D. R.; Springer, J. P. J. Org. Chem. 1983, 48, 1147. (h) Coates, R. M.; Senter, P. D.; Baker, W. R. Ibid. 1982, 47, 3597. (i) Harding, K. E.; Clement, K. S. Ibid. 1984, 49, 3870. (j) Crisp, G. T.; Scott, W. J.; Stille, J. K. J. Am. Chem. Soc. 1984, 106, 7500. For a sample of the synthesis of natural products using the Nazarov cyclization, see: (k) (±) - Trichodine: Harding, K. E.; Clement, K. S. J. Org. Chem. 1984, 49, 3870, (l) (±)-Modhephene: Schostarcz, H.; Paquette, L. A. Tetrahedron 1981, 37, 4431. (m) (±)-Stigol: MacAlpine, G. A.; Raphael, R. A.; Shaw, A.; Taylor, A.; Wild, H. J. J. Chem. Soc., Perkin Trans. 1 1976, 410. (n) (±)-Muscone: Baumann, M.; Hoffmann, W.; Muller, N. Tetrahedron Lett. 1976, 3583. (o) (±)-Nootkatone and (±)-muscopyridine: Hiyama, T.; Shinoda, M.; Saimoto, H.; Nozaki, H. Bull. Chem. Soc. Jpn. 1981, 54, 2747. (p) Diterpenoids and sesterterpenoids: Mehta, G.; Krishnamurthy, N. J. Chem. Soc., Chem. Commun. 1986, 1319.
18. For a sample of natural products containing the cyclopentane ring system, see; (a) Paquette, L. A. Top. Curr. Chem. 1984, 119, 1. (b) Bindra, J. S.; Bindra, R. Prostaglandin Synthesis; Academic Press: New York, 1977. (c) El-Naggar, L. J.; Beal, J. L. J. Nat. Prod. 1980, 46, 649. (d) Tietze L. F. Angew. Chem. 1983, 95, 840. (e) Heathcock, C. H.; Graham, S. L.; Pirrung, M. C.; Pavlac, F.; White, C. T. Total Synthesis of Natural Products; ApSimon, J., Ed.; Wiley: New York, 1983, Vol. 5, pp 333-381. (f) Vandewalle, M.; DeClerg, P. Tetrahedron 1985, 41, 1767. (g) Paquette, L. A.; Andres, D. R.; Springer, J. P. J. Org. Chem. 1983, 48, 1147. (h) Coates, R. M.; Senter, P. D.; Baker, W. R. Ibid. 1982, 47, 3597. (i) Harding, K. E.; Clement, K. S. Ibid. 1984, 49, 3870. (j) Crisp, G. T.; Scott, W. J.; Stille, J. K. J. Am. Chem. Soc. 1984, 106, 7500. For a sample of the synthesis of natural products using the Nazarov cyclization, see: (k) (±) - Trichodine: Harding, K. E.; Clement, K. S. J. Org. Chem. 1984, 49, 3870, (l) (±)-Modhephene: Schostarcz, H.; Paquette, L. A. Tetrahedron 1981, 37, 4431. (m) (±)-Stigol: MacAlpine, G. A.; Raphael, R. A.; Shaw, A.; Taylor, A.; Wild, H. J. J. Chem. Soc., Perkin Trans. 1 1976, 410. (n) (±)-Muscone: Baumann, M.; Hoffmann, W.; Muller, N. Tetrahedron Lett. 1976, 3583. (o) (±)-Nootkatone and (±)-muscopyridine: Hiyama, T.; Shinoda, M.; Saimoto, H.; Nozaki, H. Bull. Chem. Soc. Jpn. 1981, 54, 2747. (p) Diterpenoids and sesterterpenoids: Mehta, G.; Krishnamurthy, N. J. Chem. Soc., Chem. Commun. 1986, 1319.
19. For a sample of natural products containing the cyclopentane ring system, see; (a) Paquette, L. A. Top. Curr. Chem. 1984, 119, 1. (b) Bindra, J. S.; Bindra, R. Prostaglandin Synthesis; Academic Press: New York, 1977. (c) El-Naggar, L. J.; Beal, J. L. J. Nat. Prod. 1980, 46, 649. (d) Tietze L. F. Angew. Chem. 1983, 95, 840. (e) Heathcock, C. H.; Graham, S. L.; Pirrung, M. C.; Pavlac, F.; White, C. T. Total Synthesis of Natural Products; ApSimon, J., Ed.; Wiley: New York, 1983, Vol. 5, pp 333-381. (f) Vandewalle, M.; DeClerg, P. Tetrahedron 1985, 41, 1767. (g) Paquette, L. A.; Andres, D. R.; Springer, J. P. J. Org. Chem. 1983, 48, 1147. (h) Coates, R. M.; Senter, P. D.; Baker, W. R. Ibid. 1982, 47, 3597. (i) Harding, K. E.; Clement, K. S. Ibid. 1984, 49, 3870. (j) Crisp, G. T.; Scott, W. J.; Stille, J. K. J. Am. Chem. Soc. 1984, 106, 7500. For a sample of the synthesis of natural products using the Nazarov cyclization, see: (k) (±) - Trichodine: Harding, K. E.; Clement, K. S. J. Org. Chem. 1984, 49, 3870, (l) (±)-Modhephene: Schostarcz, H.; Paquette, L. A. Tetrahedron 1981, 37, 4431. (m) (±)-Stigol: MacAlpine, G. A.; Raphael, R. A.; Shaw, A.; Taylor, A.; Wild, H. J. J. Chem. Soc., Perkin Trans. 1 1976, 410. (n) (±)-Muscone: Baumann, M.; Hoffmann, W.; Muller, N. Tetrahedron Lett. 1976, 3583. (o) (±)-Nootkatone and (±)-muscopyridine: Hiyama, T.; Shinoda, M.; Saimoto, H.; Nozaki, H. Bull. Chem. Soc. Jpn. 1981, 54, 2747. (p) Diterpenoids and sesterterpenoids: Mehta, G.; Krishnamurthy, N. J. Chem. Soc., Chem. Commun. 1986, 1319.
20. For a sample of natural products containing the cyclopentane ring system, see; (a) Paquette, L. A. Top. Curr. Chem. 1984, 119, 1. (b) Bindra, J. S.; Bindra, R. Prostaglandin Synthesis; Academic Press: New York, 1977. (c) El-Naggar, L. J.; Beal, J. L. J. Nat. Prod. 1980, 46, 649. (d) Tietze L. F. Angew. Chem. 1983, 95, 840. (e) Heathcock, C. H.; Graham, S. L.; Pirrung, M. C.; Pavlac, F.; White, C. T. Total Synthesis of Natural Products; ApSimon, J., Ed.; Wiley: New York, 1983, Vol. 5, pp 333-381. (f) Vandewalle, M.; DeClerg, P. Tetrahedron 1985, 41, 1767. (g) Paquette, L. A.; Andres, D. R.; Springer, J. P. J. Org. Chem. 1983, 48, 1147. (h) Coates, R. M.; Senter, P. D.; Baker, W. R. Ibid. 1982, 47, 3597. (i) Harding, K. E.; Clement, K. S. Ibid. 1984, 49, 3870. (j) Crisp, G. T.; Scott, W. J.; Stille, J. K. J. Am. Chem. Soc. 1984, 106, 7500. For a sample of the synthesis of natural products using the Nazarov cyclization, see: (k) (±) - Trichodine: Harding, K. E.; Clement, K. S. J. Org. Chem. 1984, 49, 3870, (l) (±)-Modhephene: Schostarcz, H.; Paquette, L. A. Tetrahedron 1981, 37, 4431. (m) (±)-Stigol: MacAlpine, G. A.; Raphael, R. A.; Shaw, A.; Taylor, A.; Wild, H. J. J. Chem. Soc., Perkin Trans. 1 1976, 410. (n) (±)-Muscone: Baumann, M.; Hoffmann, W.; Muller, N. Tetrahedron Lett. 1976, 3583. (o) (±)-Nootkatone and (±)-muscopyridine: Hiyama, T.; Shinoda, M.; Saimoto, H.; Nozaki, H. Bull. Chem. Soc. Jpn. 1981, 54, 2747. (p) Diterpenoids and sesterterpenoids: Mehta, G.; Krishnamurthy, N. J. Chem. Soc., Chem. Commun. 1986, 1319.
21. For a sample of natural products containing the cyclopentane ring system, see; (a) Paquette, L. A. Top. Curr. Chem. 1984, 119, 1. (b) Bindra, J. S.; Bindra, R. Prostaglandin Synthesis; Academic Press: New York, 1977. (c) El-Naggar, L. J.; Beal, J. L. J. Nat. Prod. 1980, 46, 649. (d) Tietze L. F. Angew. Chem. 1983, 95, 840. (e) Heathcock, C. H.; Graham, S. L.; Pirrung, M. C.; Pavlac, F.; White, C. T. Total Synthesis of Natural Products; ApSimon, J., Ed.; Wiley: New York, 1983, Vol. 5, pp 333-381. (f) Vandewalle, M.; DeClerg, P. Tetrahedron 1985, 41, 1767. (g) Paquette, L. A.; Andres, D. R.; Springer, J. P. J. Org. Chem. 1983, 48, 1147. (h) Coates, R. M.; Senter, P. D.; Baker, W. R. Ibid. 1982, 47, 3597. (i) Harding, K. E.; Clement, K. S. Ibid. 1984, 49, 3870. (j) Crisp, G. T.; Scott, W. J.; Stille, J. K. J. Am. Chem. Soc. 1984, 106, 7500. For a sample of the synthesis of natural products using the Nazarov cyclization, see: (k) (±) - Trichodine: Harding, K. E.; Clement, K. S. J. Org. Chem. 1984, 49, 3870, (l) (±)-Modhephene: Schostarcz, H.; Paquette, L. A. Tetrahedron 1981, 37, 4431. (m) (±)-Stigol: MacAlpine, G. A.; Raphael, R. A.; Shaw, A.; Taylor, A.; Wild, H. J. J. Chem. Soc., Perkin Trans. 1 1976, 410. (n) (±)-Muscone: Baumann, M.; Hoffmann, W.; Muller, N. Tetrahedron Lett. 1976, 3583. (o) (±)-Nootkatone and (±)-muscopyridine: Hiyama, T.; Shinoda, M.; Saimoto, H.; Nozaki, H. Bull. Chem. Soc. Jpn. 1981, 54, 2747. (p) Diterpenoids and sesterterpenoids: Mehta, G.; Krishnamurthy, N. J. Chem. Soc., Chem. Commun. 1986, 1319.
22. For a sample of natural products containing the cyclopentane ring system, see; (a) Paquette, L. A. Top. Curr. Chem. 1984, 119, 1. (b) Bindra, J. S.; Bindra, R. Prostaglandin Synthesis; Academic Press: New York, 1977. (c) El-Naggar, L. J.; Beal, J. L. J. Nat. Prod. 1980, 46, 649. (d) Tietze L. F. Angew. Chem. 1983, 95, 840. (e) Heathcock, C. H.; Graham, S. L.; Pirrung, M. C.; Pavlac, F.; White, C. T. Total Synthesis of Natural Products; ApSimon, J., Ed.; Wiley: New York, 1983, Vol. 5, pp 333-381. (f) Vandewalle, M.; DeClerg, P. Tetrahedron 1985, 41, 1767. (g) Paquette, L. A.; Andres, D. R.; Springer, J. P. J. Org. Chem. 1983, 48, 1147. (h) Coates, R. M.; Senter, P. D.; Baker, W. R. Ibid. 1982, 47, 3597. (i) Harding, K. E.; Clement, K. S. Ibid. 1984, 49, 3870. (j) Crisp, G. T.; Scott, W. J.; Stille, J. K. J. Am. Chem. Soc. 1984, 106, 7500. For a sample of the synthesis of natural products using the Nazarov cyclization, see: (k) (±) - Trichodine: Harding, K. E.; Clement, K. S. J. Org. Chem. 1984, 49, 3870, (l) (±)-Modhephene: Schostarcz, H.; Paquette, L. A. Tetrahedron 1981, 37, 4431. (m) (±)-Stigol: MacAlpine, G. A.; Raphael, R. A.; Shaw, A.; Taylor, A.; Wild, H. J. J. Chem. Soc., Perkin Trans. 1 1976, 410. (n) (±)-Muscone: Baumann, M.; Hoffmann, W.; Muller, N. Tetrahedron Lett. 1976, 3583. (o) (±)-Nootkatone and (±)-muscopyridine: Hiyama, T.; Shinoda, M.; Saimoto, H.; Nozaki, H. Bull. Chem. Soc. Jpn. 1981, 54, 2747. (p) Diterpenoids and sesterterpenoids: Mehta, G.; Krishnamurthy, N. J. Chem. Soc., Chem. Commun. 1986, 1319.
23. For a sample of natural products containing the cyclopentane ring system, see; (a) Paquette, L. A. Top. Curr. Chem. 1984, 119, 1. (b) Bindra, J. S.; Bindra, R. Prostaglandin Synthesis; Academic Press: New York, 1977. (c) El-Naggar, L. J.; Beal, J. L. J. Nat. Prod. 1980, 46, 649. (d) Tietze L. F. Angew. Chem. 1983, 95, 840. (e) Heathcock, C. H.; Graham, S. L.; Pirrung, M. C.; Pavlac, F.; White, C. T. Total Synthesis of Natural Products; ApSimon, J., Ed.; Wiley: New York, 1983, Vol. 5, pp 333-381. (f) Vandewalle, M.; DeClerg, P. Tetrahedron 1985, 41, 1767. (g) Paquette, L. A.; Andres, D. R.; Springer, J. P. J. Org. Chem. 1983, 48, 1147. (h) Coates, R. M.; Senter, P. D.; Baker, W. R. Ibid. 1982, 47, 3597. (i) Harding, K. E.; Clement, K. S. Ibid. 1984, 49, 3870. (j) Crisp, G. T.; Scott, W. J.; Stille, J. K. J. Am. Chem. Soc. 1984, 106, 7500. For a sample of the synthesis of natural products using the Nazarov cyclization, see: (k) (±) - Trichodine: Harding, K. E.; Clement, K. S. J. Org. Chem. 1984, 49, 3870, (l) (±)-Modhephene: Schostarcz, H.; Paquette, L. A. Tetrahedron 1981, 37, 4431. (m) (±)-Stigol: MacAlpine, G. A.; Raphael, R. A.; Shaw, A.; Taylor, A.; Wild, H. J. J. Chem. Soc., Perkin Trans. 1 1976, 410. (n) (±)-Muscone: Baumann, M.; Hoffmann, W.; Muller, N. Tetrahedron Lett. 1976, 3583. (o) (±)-Nootkatone and (±)-muscopyridine: Hiyama, T.; Shinoda, M.; Saimoto, H.; Nozaki, H. Bull. Chem. Soc. Jpn. 1981, 54, 2747. (p) Diterpenoids and sesterterpenoids: Mehta, G.; Krishnamurthy, N. J. Chem. Soc., Chem. Commun. 1986, 1319.
24. For a sample of natural products containing the cyclopentane ring system, see; (a) Paquette, L. A. Top. Curr. Chem. 1984, 119, 1. (b) Bindra, J. S.; Bindra, R. Prostaglandin Synthesis; Academic Press: New York, 1977. (c) El-Naggar, L. J.; Beal, J. L. J. Nat. Prod. 1980, 46, 649. (d) Tietze L. F. Angew. Chem. 1983, 95, 840. (e) Heathcock, C. H.; Graham, S. L.; Pirrung, M. C.; Pavlac, F.; White, C. T. Total Synthesis of Natural Products; ApSimon, J., Ed.; Wiley: New York, 1983, Vol. 5, pp 333-381. (f) Vandewalle, M.; DeClerg, P. Tetrahedron 1985, 41, 1767. (g) Paquette, L. A.; Andres, D. R.; Springer, J. P. J. Org. Chem. 1983, 48, 1147. (h) Coates, R. M.; Senter, P. D.; Baker, W. R. Ibid. 1982, 47, 3597. (i) Harding, K. E.; Clement, K. S. Ibid. 1984, 49, 3870. (j) Crisp, G. T.; Scott, W. J.; Stille, J. K. J. Am. Chem. Soc. 1984, 106, 7500. For a sample of the synthesis of natural products using the Nazarov cyclization, see: (k) (±) - Trichodine: Harding, K. E.; Clement, K. S. J. Org. Chem. 1984, 49, 3870, (l) (±)-Modhephene: Schostarcz, H.; Paquette, L. A. Tetrahedron 1981, 37, 4431. (m) (±)-Stigol: MacAlpine, G. A.; Raphael, R. A.; Shaw, A.; Taylor, A.; Wild, H. J. J. Chem. Soc., Perkin Trans. 1 1976, 410. (n) (±)-Muscone: Baumann, M.; Hoffmann, W.; Muller, N. Tetrahedron Lett. 1976, 3583. (o) (±)-Nootkatone and (±)-muscopyridine: Hiyama, T.; Shinoda, M.; Saimoto, H.; Nozaki, H. Bull. Chem. Soc. Jpn. 1981, 54, 2747. (p) Diterpenoids and sesterterpenoids: Mehta, G.; Krishnamurthy, N. J. Chem. Soc., Chem. Commun. 1986, 1319.
25. For a sample of natural products containing the cyclopentane ring system, see; (a) Paquette, L. A. Top. Curr. Chem. 1984, 119, 1. (b) Bindra, J. S.; Bindra, R. Prostaglandin Synthesis; Academic Press: New York, 1977. (c) El-Naggar, L. J.; Beal, J. L. J. Nat. Prod. 1980, 46, 649. (d) Tietze L. F. Angew. Chem. 1983, 95, 840. (e) Heathcock, C. H.; Graham, S. L.; Pirrung, M. C.; Pavlac, F.; White, C. T. Total Synthesis of Natural Products; ApSimon, J., Ed.; Wiley: New York, 1983, Vol. 5, pp 333-381. (f) Vandewalle, M.; DeClerg, P. Tetrahedron 1985, 41, 1767. (g) Paquette, L. A.; Andres, D. R.; Springer, J. P. J. Org. Chem. 1983, 48, 1147. (h) Coates, R. M.; Senter, P. D.; Baker, W. R. Ibid. 1982, 47, 3597. (i) Harding, K. E.; Clement, K. S. Ibid. 1984, 49, 3870. (j) Crisp, G. T.; Scott, W. J.; Stille, J. K. J. Am. Chem. Soc. 1984, 106, 7500. For a sample of the synthesis of natural products using the Nazarov cyclization, see: (k) (±) - Trichodine: Harding, K. E.; Clement, K. S. J. Org. Chem. 1984, 49, 3870, (l) (±)-Modhephene: Schostarcz, H.; Paquette, L. A. Tetrahedron 1981, 37, 4431. (m) (±)-Stigol: MacAlpine, G. A.; Raphael, R. A.; Shaw, A.; Taylor, A.; Wild, H. J. J. Chem. Soc., Perkin Trans. 1 1976, 410. (n) (±)-Muscone: Baumann, M.; Hoffmann, W.; Muller, N. Tetrahedron Lett. 1976, 3583. (o) (±)-Nootkatone and (±)-muscopyridine: Hiyama, T.; Shinoda, M.; Saimoto, H.; Nozaki, H. Bull. Chem. Soc. Jpn. 1981, 54, 2747. (p) Diterpenoids and sesterterpenoids: Mehta, G.; Krishnamurthy, N. J. Chem. Soc., Chem. Commun. 1986, 1319.
26. For a sample of natural products containing the cyclopentane ring system, see; (a) Paquette, L. A. Top. Curr. Chem. 1984, 119, 1. (b) Bindra, J. S.; Bindra, R. Prostaglandin Synthesis; Academic Press: New York, 1977. (c) El-Naggar, L. J.; Beal, J. L. J. Nat. Prod. 1980, 46, 649. (d) Tietze L. F. Angew. Chem. 1983, 95, 840. (e) Heathcock, C. H.; Graham, S. L.; Pirrung, M. C.; Pavlac, F.; White, C. T. Total Synthesis of Natural Products; ApSimon, J., Ed.; Wiley: New York, 1983, Vol. 5, pp 333-381. (f) Vandewalle, M.; DeClerg, P. Tetrahedron 1985, 41, 1767. (g) Paquette, L. A.; Andres, D. R.; Springer, J. P. J. Org. Chem. 1983, 48, 1147. (h) Coates, R. M.; Senter, P. D.; Baker, W. R. Ibid. 1982, 47, 3597. (i) Harding, K. E.; Clement, K. S. Ibid. 1984, 49, 3870. (j) Crisp, G. T.; Scott, W. J.; Stille, J. K. J. Am. Chem. Soc. 1984, 106, 7500. For a sample of the synthesis of natural products using the Nazarov cyclization, see: (k) (±) - Trichodine: Harding, K. E.; Clement, K. S. J. Org. Chem. 1984, 49, 3870, (l) (±)-Modhephene: Schostarcz, H.; Paquette, L. A. Tetrahedron 1981, 37, 4431. (m) (±)-Stigol: MacAlpine, G. A.; Raphael, R. A.; Shaw, A.; Taylor, A.; Wild, H. J. J. Chem. Soc., Perkin Trans. 1 1976, 410. (n) (±)-Muscone: Baumann, M.; Hoffmann, W.; Muller, N. Tetrahedron Lett. 1976, 3583. (o) (±)-Nootkatone and (±)-muscopyridine: Hiyama, T.; Shinoda, M.; Saimoto, H.; Nozaki, H. Bull. Chem. Soc. Jpn. 1981, 54, 2747. (p) Diterpenoids and sesterterpenoids: Mehta, G.; Krishnamurthy, N. J. Chem. Soc., Chem. Commun. 1986, 1319.
27. For a sample of natural products containing the cyclopentane ring system, see; (a) Paquette, L. A. Top. Curr. Chem. 1984, 119, 1. (b) Bindra, J. S.; Bindra, R. Prostaglandin Synthesis; Academic Press: New York, 1977. (c) El-Naggar, L. J.; Beal, J. L. J. Nat. Prod. 1980, 46, 649. (d) Tietze L. F. Angew. Chem. 1983, 95, 840. (e) Heathcock, C. H.; Graham, S. L.; Pirrung, M. C.; Pavlac, F.; White, C. T. Total Synthesis of Natural Products; ApSimon, J., Ed.; Wiley: New York, 1983, Vol. 5, pp 333-381. (f) Vandewalle, M.; DeClerg, P. Tetrahedron 1985, 41, 1767. (g) Paquette, L. A.; Andres, D. R.; Springer, J. P. J. Org. Chem. 1983, 48, 1147. (h) Coates, R. M.; Senter, P. D.; Baker, W. R. Ibid. 1982, 47, 3597. (i) Harding, K. E.; Clement, K. S. Ibid. 1984, 49, 3870. (j) Crisp, G. T.; Scott, W. J.; Stille, J. K. J. Am. Chem. Soc. 1984, 106, 7500. For a sample of the synthesis of natural products using the Nazarov cyclization, see: (k) (±) - Trichodine: Harding, K. E.; Clement, K. S. J. Org. Chem. 1984, 49, 3870, (l) (±)-Modhephene: Schostarcz, H.; Paquette, L. A. Tetrahedron 1981, 37, 4431. (m) (±)-Stigol: MacAlpine, G. A.; Raphael, R. A.; Shaw, A.; Taylor, A.; Wild, H. J. J. Chem. Soc., Perkin Trans. 1 1976, 410. (n) (±)-Muscone: Baumann, M.; Hoffmann, W.; Muller, N. Tetrahedron Lett. 1976, 3583. (o) (±)-Nootkatone and (±)-muscopyridine: Hiyama, T.; Shinoda, M.; Saimoto, H.; Nozaki, H. Bull. Chem. Soc. Jpn. 1981, 54, 2747. (p) Diterpenoids and sesterterpenoids: Mehta, G.; Krishnamurthy, N. J. Chem. Soc., Chem. Commun. 1986, 1319.
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40. Charges for the RHF/3-21G(*)-optimized geometries and MP2/ 6-31G** single points differ; however, the trend remains the same at all levels.