Synthesis of (+)-siphonarienone: Asymmetric alkylation using a chiral benzopyrano-isoxazolidine auxiliary

Tetrahedron Letters

Volumn 37, Issue 7, 1996, Pages 1081-1084

  Abiko, Atsushi ^b   Masamune, Satoru ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

^b KAO CORPORATION   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ALKANEDIOL DERIVATIVE; SIPHONARIENONE; UNCLASSIFIED DRUG;

ARTICLE; CHIRALITY; DRUG SYNTHESIS; REACTION ANALYSIS; TECHNIQUE;

EID: 0030041259     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/0040-4039(95)02353-4     Document Type: Article

References (13)

1. Abiko, A.; Moriya, O.; Filla, S. A.; Masamune, S. Angew. Chem. Int. Ed. Engl. 1995, 34, 793.
2. Evans, D. A.; Dow, R. L.; Shih, T. L.; Takacs, J. M.; Zahler, R. J. J. Am. Chem. Soc. 1990, 112, 5290. White, D. J.; Johnson, A. T. J. Org. Chem. 1994, 59, 3347.
3. Evans, D. A.; Dow, R. L.; Shih, T. L.; Takacs, J. M.; Zahler, R. J. J. Am. Chem. Soc. 1990, 112, 5290. White, D. J.; Johnson, A. T. J. Org. Chem. 1994, 59, 3347.
4. 3).
5. (S)-2 was prepared in multi-gram quantity by resolution of (±)-2-methylpentanoic acid with the (-)-isoxazolidine, followed by reduction. (equation presented)
6. After warming an enolate solution (-78∼-30 °C, 1 h), 1 was recovered in 75 % yield along with fragmentation products, from which 20 was isolated. (equation presented)
7. Nahm, S.; Weinreb S. M. Tetrahedron Lett. 1981, 22, 3815.
8. Masamune, S.; Choy, W.; Petersen, J. S.; Sita, L. R. Angew. Chem. Int. Ed. Engl. 1985, 24, 1.; Sato, T.; Abiko, A.; Masamune, S. J. Synth. Org. Chem. Jpn. 1986, 44, 309, 384.
9. Masamune, S.; Choy, W.; Petersen, J. S.; Sita, L. R. Angew. Chem. Int. Ed. Engl. 1985, 24, 1.; Sato, T.; Abiko, A.; Masamune, S. J. Synth. Org. Chem. Jpn. 1986, 44, 309, 384.
10. 10 was converted to the corresponding known diol: Chiarello, J.; Joullie. M. M. Synth. Commun. 1989, 19, 3379. ent-12: Tsuda, M.; Sasaki, T.; Kobayashi, J. J. Org. Chem. 1994, 59, 3734.
11. 10 was converted to the corresponding known diol: Chiarello, J.; Joullie. M. M. Synth. Commun. 1989, 19, 3379. ent-12: Tsuda, M.; Sasaki, T.; Kobayashi, J. J. Org. Chem. 1994, 59, 3734.
12. The triflate of anti-alcohol 15 was prepared in diethyl ether at -78 °C and 2.5 eq. of the enolate solution in diethyl ether was transferred via cannula.
13. 13C NMR δ 69.0, 68.0, 41.4, 40.6, 33.0, 32.9, 27.2, 20.3, 17.2, 16.5.