Allylboration of alkenes with allyldihaloboranes

Journal of the American Chemical Society

Volumn 118, Issue 41, 1996, Pages 9986-9987

  Singleton, Daniel A ^a   Waller, Stephen C ^a   Zhang, Zongren ^a   Frantz, Doug E ^a   Leung, Shun Wang ^a  

^a TEXAS A AND M UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALLYL COMPOUND; POLYENE;

ARTICLE; DRUG SYNTHESIS; REACTION ANALYSIS;

EID: 0029958117     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja961616k     Document Type: Article

References (25)

1. Normant, J. F.; Alexakis, A. Synthesis 1981, 841. Negishi, E. Acc. Chem. Res. 1987, 20, 65-72.
2. Normant, J. F.; Alexakis, A. Synthesis 1981, 841. Negishi, E. Acc. Chem. Res. 1987, 20, 65-72.
3. Shaughnessy, K. H.; Waymouth, R. M. J. Am. Chem. Soc. 1995, 117, 5873-4. Negishi, E.; Jensen, M. D.; Kondakov, D. Y.; Wang, S. J. Am. Chem. Soc. 1994, 116, 8404. Zhang, Y.; Negishi, E. J. Am. Chem. Soc. 1989, 111, 3454.
4. Shaughnessy, K. H.; Waymouth, R. M. J. Am. Chem. Soc. 1995, 117, 5873-4. Negishi, E.; Jensen, M. D.; Kondakov, D. Y.; Wang, S. J. Am. Chem. Soc. 1994, 116, 8404. Zhang, Y.; Negishi, E. J. Am. Chem. Soc. 1989, 111, 3454.
5. Shaughnessy, K. H.; Waymouth, R. M. J. Am. Chem. Soc. 1995, 117, 5873-4. Negishi, E.; Jensen, M. D.; Kondakov, D. Y.; Wang, S. J. Am. Chem. Soc. 1994, 116, 8404. Zhang, Y.; Negishi, E. J. Am. Chem. Soc. 1989, 111, 3454.
6. Richey, H. G., Jr.; Erickson, W. F.; Heyn, A. S. Tetrahedron Lett. 1971, 48, 2183-2186. Eisch, J. J.; Merkley, J. H.; Galle, J. E. J. Am. Chem. Soc. 1979, 101, 1148-1155. See also: Hoveyda, A. H.; Xu, Z.; Morken, J. P.; Houri, A. F. J. Am. Chem. Soc. 1991, 113, 8950.
7. Richey, H. G., Jr.; Erickson, W. F.; Heyn, A. S. Tetrahedron Lett. 1971, 48, 2183-2186. Eisch, J. J.; Merkley, J. H.; Galle, J. E. J. Am. Chem. Soc. 1979, 101, 1148-1155. See also: Hoveyda, A. H.; Xu, Z.; Morken, J. P.; Houri, A. F. J. Am. Chem. Soc. 1991, 113, 8950.
8. Richey, H. G., Jr.; Erickson, W. F.; Heyn, A. S. Tetrahedron Lett. 1971, 48, 2183-2186. Eisch, J. J.; Merkley, J. H.; Galle, J. E. J. Am. Chem. Soc. 1979, 101, 1148-1155. See also: Hoveyda, A. H.; Xu, Z.; Morken, J. P.; Houri, A. F. J. Am. Chem. Soc. 1991, 113, 8950.
9. Lehmkuhl, H. Bull. Chim. Soc. Fr. II 1981, 87-95.
10. Dzhemilev, U. M.; Vostrikova, O. S. J. Organomet. Chem. 1985, 285, 43-51. Hoveyda, A. H.; Xu, Z. J. Am. Chem. Soc. 1991, 113, 5079. Takahashi, T.; Seki, T.; Nitto, Y.; Saburi, M.; Roussel, C. J.; Negishi, E. J. Am. Chem. Soc. 1991, 113, 6266-6268.
11. Dzhemilev, U. M.; Vostrikova, O. S. J. Organomet. Chem. 1985, 285, 43-51. Hoveyda, A. H.; Xu, Z. J. Am. Chem. Soc. 1991, 113, 5079. Takahashi, T.; Seki, T.; Nitto, Y.; Saburi, M.; Roussel, C. J.; Negishi, E. J. Am. Chem. Soc. 1991, 113, 6266-6268.
12. Dzhemilev, U. M.; Vostrikova, O. S. J. Organomet. Chem. 1985, 285, 43-51. Hoveyda, A. H.; Xu, Z. J. Am. Chem. Soc. 1991, 113, 5079. Takahashi, T.; Seki, T.; Nitto, Y.; Saburi, M.; Roussel, C. J.; Negishi, E. J. Am. Chem. Soc. 1991, 113, 6266-6268.
13. Nakamura, E.; Nakamura, M.; Miyachi, Y.; Koga, N.; Morokuma, K. J. Am. Chem. Soc. 1993, 115, 99.
14. Lehmkuhl, H. In Organometallics in Organic Synthesis; De Meijere, A., Dieck, T., Eds.; Springer-Verlag; New York, 1987; pp 185-202. Nakamura, M.; Arai, M.; Nakamura, E. J. Am. Chem. Soc. 1995, 117, 1179-1180. Yamamoto, Y.; Asao, N. Chem. Rev. 1993, 93, 2207-2293.
15. Lehmkuhl, H. In Organometallics in Organic Synthesis; De Meijere, A., Dieck, T., Eds.; Springer-Verlag; New York, 1987; pp 185-202. Nakamura, M.; Arai, M.; Nakamura, E. J. Am. Chem. Soc. 1995, 117, 1179-1180. Yamamoto, Y.; Asao, N. Chem. Rev. 1993, 93, 2207-2293.
16. Lehmkuhl, H. In Organometallics in Organic Synthesis; De Meijere, A., Dieck, T., Eds.; Springer-Verlag; New York, 1987; pp 185-202. Nakamura, M.; Arai, M.; Nakamura, E. J. Am. Chem. Soc. 1995, 117, 1179-1180. Yamamoto, Y.; Asao, N. Chem. Rev. 1993, 93, 2207-2293.
17. Oppolzer, W. Angew. Chem., Int. Ed. Engl. 1989, 28, 38-52.
18. For reviews, see: Mikhailov. B. M. Russ. Chem. Rev. 1976, 45, 557. Bubnov, Y. N. Pure Appl. Chem. 1987, 59, 895.
19. For reviews, see: Mikhailov. B. M. Russ. Chem. Rev. 1976, 45, 557. Bubnov, Y. N. Pure Appl. Chem. 1987, 59, 895.
20. Mikhailov, B. M.; Bubnov, Y. N. Zh. Obshch. Khim. 1971, 41, 2039.
21. Harston, P.; Wardell, J. L.; Marton, D.; Tagliavini, G.; Smith, P. J. Inorg. Chim. Acta 1989, 162, 245-50.
22. 1H NMR of the internal double bond could be simulated using a vinylic vicinal coupling constant of 10 Hz, indicative of the Z stereochemistry. The structure of 18 (R = H) was further confirmed by hydrolysis to the known alcohol (Andrews, G. D. Macromolecules 1984, 17, 1624-1626). The stereochemistry of 24 was assigned from a similarity of its NMR spectrum to that of the known cis-2-methyl-3-cyclohexen-1-ol (Singleton, D. A.; Martinez, J. P.; Watson, J. V.; Ndip, G. M Tetrahedron 1992, 48, 5831). The stereochemistry of 14 could only be speculatively assigned on the basis of the stereospecificity of the reaction (see text) and the observation of syn addition in the other reactions.
23. 1H NMR of the internal double bond could be simulated using a vinylic vicinal coupling constant of 10 Hz, indicative of the Z stereochemistry. The structure of 18 (R = H) was further confirmed by hydrolysis to the known alcohol (Andrews, G. D. Macromolecules 1984, 17, 1624-1626). The stereochemistry of 24 was assigned from a similarity of its NMR spectrum to that of the known cis-2-methyl-3-cyclohexen-1-ol (Singleton, D. A.; Martinez, J. P.; Watson, J. V.; Ndip, G. M Tetrahedron 1992, 48, 5831). The stereochemistry of 14 could only be speculatively assigned on the basis of the stereospecificity of the reaction (see text) and the observation of syn addition in the other reactions.
24. 2 and 5 mL of THF to the cooled mixture, which was then stirred at 25 °C overnight. After a normal ethereal extraction, chromatography of the residue on a 0.75 in. × 14 in. silica gel column with 6% EtOAc in hexanes as eluent afforded 0.295 g (70%) of 10.
25. E = -1138.21609. Structure 25 is fully optimized and exhibited one imaginary frequency. The predicted activation energy is 31.0 kcal/mol. For comparison calculations on simple ene reactions, see: Loncharich, R. J.; Houk, K. N. J. Am. Chem. Soc. 1987, 109, 6947.