Intramolecular Diels-Alder reactions of alkenylboranes a stereoselective route to functionalized bicycle[4.3.0] nonenes

Tetrahedron Letters

Volumn 38, Issue 21, 1997, Pages 3699-3702

  Batey, Robert A ^a   Lin, Denny ^a   Wong, Andrew ^a   Hayhoe, Christina L S ^a  

^a UNIVERSITY OF TORONTO   (Canada)

Author keywords

Alkenylbornae; E Enol dienophile equivalent; Hydroboration; Intramolecular Diels Alder reaction; Masked dienophile

Indexed keywords

BICYCLO COMPOUND; BICYCLO[4.3.0]NONANE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; DRUG SYNTHESIS; IN VITRO STUDY; METHODOLOGY; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0030940360     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(97)00716-8     Document Type: Article

References (27)

1. For reviews on intramolecular Diels-Alder reactions,see:(a) Roush, W. R. in Comprehensive Organic Synthesis, Trost, B. M, Fleming, I., Paquette, L. A., Eds.; Pergamon: Oxford, 1991, Vol. 5, 513-550;
2. (b) Carruthers, W. Cycloaddition Reactions in Organic Synthesis, Pergamon: Oxford, 1990;
3. (c) Craig, D. Chem. Soc. Rev. 1987, 16, 187-238;
4. (d) Fallis A. G. Can. J. Chem. 1984, 62, 183-234.
5. Batey, R. A.; Pedram, B.; Yong, K.; Baquer, G. Tetrahedron Lett. 1996, 37, 6847-6850.
6. This work was presented at the 7th Ontario-Quebec Minisymposium, University of Waterloo, Ontario, October 1996, "Recent Advances in Intramolecular Diels-Alder Cycloaddition Chemistry"; and at the Canadian Society for Chemistry Meeting, Memorial University, St. John's, Newfoundland, June 1996, "Intramolecular Diels-Alder Reactions of Alkenylboranes."
7. (a) Matteson, D. S. Stereodirected Synthesis with Organoboranes, Springer-Verlag: Berlin, 1995;
8. (b) Pelter, A.; Smith, K.; Brown, H. C. Borane Reagents, Academic: London, 1988.
9. Matteson, D. S.; Waldbillig, J. O. J. Org. Chem. 1963, 28, 366-369.
10. (a) Singleton, D. A.; Martinez, J. P. J. Am. Chem. Soc. 1990, 772, 7423-7424;
11. (b) Singleton, D. A.; Martinez, J. P.; Ndip, G. M. J. Org. Chem. 1992, 57, 5768-5771;
12. (c) Singleton, D. A.; Martinez, J. P.; Watson, J. V. Tetrahedron Lett. 1992, 33, 1017-1020.
13. Singleton, D. A.; Lee, Y.-K. Tetrahedron Lett. 1995, 36, 3473-3476.
14. Compounds 6a and 6b were synthesized by propargylation of the corresponding sodium alkoxides. Compound 6c was synthesized by standard malonate alkylation techniques.
15. Dieneyne 6a-c (1.9 mmol) was added dropwise to a suspension of dicyclohexylborane (2.0 mmol in 4 ml of THF). After stirring for 2 h, BHT (0.1 mmol) in freshly distilled benzene (50 mL) was added to the reaction and the reaction mixture was heated at reflux for 17-20 h. After cooling to room temperature, trimethylamine-N-oxide dihydrate (6.5 mmol) was added and the reaction was reheated to reflux for 24 h. Upon cooling to room temperature, distilled water (20 mL) was added and the reaction mixture was heated to 60 °C for 30 min. Aqueous work-up and purification by flash column chromatography (silica gel, EtOAc /hexanes) afforded the desired bicyclo[4.3.0]alkenols 7a-c. In each case only a single diastereomer was observed by NMR and t.l.c.
16. 3) δ 134.94, 122.77, 72.59, 70.64, 70.00, 45.22, 45.09, 37.55, 14.53; HRMS (EI) m/e calcd. (M-H+) 153.0915, found 153.0911.
17. Brown, H. C.; Gupta, S. K. J Am. Chem. Soc. 1975, 97, 5249-5255.
18. (a) Lin, Y.-T.; Houk, K. N. Tetrahedron Lett. 1985, 26, 2269-2272;
19. (b) Roush, W. R.; Gillis, H. R.; Ko, A. I. J. Am. Chem. Soc. 1982, 104, 2269-2283;
20. (c) Kurth, M. J.; O'Brien, M. J.; Hope, H.; Yanuck, M. J. Org. Chem. 1985, 50, 2626-2632;
21. (d) Hertel, R.; Mattay, J.; Runsink, J. J. Am. Chem. Soc. 1991, 113, 657-665;
22. (e) Roush, W. R.; Hall, S. E. J. Am. Chem. Soc. 1981, 103, 5200-5211;
23. (f) Boeckman, Jr., R. K.; Demko, D. M. J. Org. Chem. 1982, 47, 1789-1792.
24. The selectivity observed in the Cycloaddition of 11f, is presumably complicated by considerable diradical character for the transition states.
25. Singleton, D. A. J. Am. Chem. Soc. 1992, 114, 6563-6564.
26. Chou, T.-S.; Tso H.-H., Chang, L.-J. J. Chem. Soc., Chem. Commun. 1985, 236-237.
27. Trans-fused products similar to that of tricycle 7b are also formed from the allylated analog of 6b, see: Burke, S. D.; Smith Strickland, S. M.; Powner, T. H. J. Org. Chem. 1983, 48, 454-459.