Carbocyclic ring construction via intramolecular ionic Diels-Alder reactions of in situ -generated, heteroatom-stabilized allyl cations in highly polar media

Journal of the American Chemical Society

Volumn 118, Issue 8, 1996, Pages 2095-2096

  Grieco, Paul A ^a   Kaufman, Michael D ^a   Daeuble, John F ^a   Saito, Naoki ^a  

^a INDIANA UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

POLYCYCLIC HYDROCARBON; STEROID;

ARTICLE; DRUG SYNTHESIS; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0029965940     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9531992     Document Type: Article

References (22)

1. For reviews on the intramolecular Diels-Alder reaction, see: Ciganek, E. Org. React. 1984, 32, 1. Roush, W. R In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds; Pergamon: Oxford. 1991: Vol. 5, Chapter 4.4. pp 513-550.
2. For reviews on the intramolecular Diels-Alder reaction, see: Ciganek, E. Org. React. 1984, 32, 1. Roush, W. R In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds; Pergamon: Oxford. 1991: Vol. 5, Chapter 4.4. pp 513-550.
3. For examples of intramolecular tonic Diels-Alder reactions, see: (a) Roush, W. R.; Gillis, H. R, Essenfeld, A. P. J. Org. Chem. 1984, 49, 4674. (b) Gassman, P. G.: Singleton, D. A. J. Org. Chem. 1986, 51, 3075. Gassman, P. G.: Gorman, D. B. J. Am. Chem. Soc. 1990, 112, 8623. Gassman, P. G.; Gorman, D. B. J. Am. Chem. Soc. 1990, 112, 8624. Gorman, D. B.; Gassman, P. G. J. Org. Chem. 1995, 60, 977.
4. For examples of intramolecular tonic Diels-Alder reactions, see: (a) Roush, W. R.; Gillis, H. R, Essenfeld, A. P. J. Org. Chem. 1984, 49, 4674. (b) Gassman, P. G.: Singleton, D. A. J. Org. Chem. 1986, 51, 3075. Gassman, P. G.: Gorman, D. B. J. Am. Chem. Soc. 1990, 112, 8623. Gassman, P. G.; Gorman, D. B. J. Am. Chem. Soc. 1990, 112, 8624. Gorman, D. B.; Gassman, P. G. J. Org. Chem. 1995, 60, 977.
5. For examples of intramolecular tonic Diels-Alder reactions, see: (a) Roush, W. R.; Gillis, H. R, Essenfeld, A. P. J. Org. Chem. 1984, 49, 4674. (b) Gassman, P. G.: Singleton, D. A. J. Org. Chem. 1986, 51, 3075. Gassman, P. G.: Gorman, D. B. J. Am. Chem. Soc. 1990, 112, 8623. Gassman, P. G.; Gorman, D. B. J. Am. Chem. Soc. 1990, 112, 8624. Gorman, D. B.; Gassman, P. G. J. Org. Chem. 1995, 60, 977.
6. For examples of intramolecular tonic Diels-Alder reactions, see: (a) Roush, W. R.; Gillis, H. R, Essenfeld, A. P. J. Org. Chem. 1984, 49, 4674. (b) Gassman, P. G.: Singleton, D. A. J. Org. Chem. 1986, 51, 3075. Gassman, P. G.: Gorman, D. B. J. Am. Chem. Soc. 1990, 112, 8623. Gassman, P. G.; Gorman, D. B. J. Am. Chem. Soc. 1990, 112, 8624. Gorman, D. B.; Gassman, P. G. J. Org. Chem. 1995, 60, 977.
7. For examples of intramolecular tonic Diels-Alder reactions, see: (a) Roush, W. R.; Gillis, H. R, Essenfeld, A. P. J. Org. Chem. 1984, 49, 4674. (b) Gassman, P. G.: Singleton, D. A. J. Org. Chem. 1986, 51, 3075. Gassman, P. G.: Gorman, D. B. J. Am. Chem. Soc. 1990, 112, 8623. Gassman, P. G.; Gorman, D. B. J. Am. Chem. Soc. 1990, 112, 8624. Gorman, D. B.; Gassman, P. G. J. Org. Chem. 1995, 60, 977.
8. For the use of highly polar media to promote Diels-Alder reactions, see: Grieco, P. A.; Nunes, J. J : Gaul, M. D. J. Am. Chem. Soc. 1990, 112, 4595. Grieco, P A.; Handy, S. T.: Beck, J. P. Tetrahedron Lett. 1994, 35, 2663. Grieco, P. A. Aldrichim, Acta 1991, 24, 59. Also see: Grieco, P. A. Organic Chemistry in Lithium Perchlorate/Diethyl Ether. In Organic Chemistry: Its Language and Its State of the Art; Kisakurek, V., Ed.: VCH. Basel, 1993; p 133.
9. For the use of highly polar media to promote Diels-Alder reactions, see: Grieco, P. A.; Nunes, J. J : Gaul, M. D. J. Am. Chem. Soc. 1990, 112, 4595. Grieco, P A.; Handy, S. T.: Beck, J. P. Tetrahedron Lett. 1994, 35, 2663. Grieco, P. A. Aldrichim, Acta 1991, 24, 59. Also see: Grieco, P. A. Organic Chemistry in Lithium Perchlorate/Diethyl Ether. In Organic Chemistry: Its Language and Its State of the Art; Kisakurek, V., Ed.: VCH. Basel, 1993; p 133.
10. For the use of highly polar media to promote Diels-Alder reactions, see: Grieco, P. A.; Nunes, J. J : Gaul, M. D. J. Am. Chem. Soc. 1990, 112, 4595. Grieco, P A.; Handy, S. T.: Beck, J. P. Tetrahedron Lett. 1994, 35, 2663. Grieco, P. A. Aldrichim, Acta 1991, 24, 59. Also see: Grieco, P. A. Organic Chemistry in Lithium Perchlorate/Diethyl Ether. In Organic Chemistry: Its Language and Its State of the Art; Kisakurek, V., Ed.: VCH. Basel, 1993; p 133.
11. For the use of highly polar media to promote Diels-Alder reactions, see: Grieco, P. A.; Nunes, J. J : Gaul, M. D. J. Am. Chem. Soc. 1990, 112, 4595. Grieco, P A.; Handy, S. T.: Beck, J. P. Tetrahedron Lett. 1994, 35, 2663. Grieco, P. A. Aldrichim, Acta 1991, 24, 59. Also see: Grieco, P. A. Organic Chemistry in Lithium Perchlorate/Diethyl Ether. In Organic Chemistry: Its Language and Its State of the Art; Kisakurek, V., Ed.: VCH. Basel, 1993; p 133.
12. Grieco, P. A.; Collins, J. I.; Henry, K. J . Jr. Tetrahedron Lett. 1992, 33, 4735.
13. o by reduction with lithium aluminum hydride in diethyl ether at 0 °C. followed by a nonaqueous workup.
14. (b) Me or Et can be substituted for i-Bu
15. The starting vinylogous esters and the 4-substituted cyclohexenones were prepared by the method of Stork Stork, G.: Danheiser, R. L. J. Org. Chem. 1973, 38, 1775.
16. 1H NMR spectra of 9, whose structure was confirmed by single-crystal X-ray analysis of the derived p-phenylbenzoate i. equation presented
17. (a) The structures for 6 and 7 were determined by single-crystal X-ray analysis of the derived bromo ether ii and alcohol iii. respectively. equation presented
18. (b) The structure of 14 was determined by single-crystal X-ray analysis.
19. 1H NMR decoupling experiments and NOE measurements (cf. iv). equation presented
20. Cf., Grieco, P. A.: Beck, J P.: Handy, S. T., Saito, N.: Daeuble, J. F. Tetrahedron Lett. 1994, 35, 6783.
21. Haynes, R K.: King, G. R.: Vonwiller, S. C. J. Org. Chem. 1994, 59, 4743.
22. Calculations indicate that 16 is more stable than 15 by 25 kcal.