A novel sulfoxide-directed route to enantiopure tetrahydrofurans: Application to the expedient formal synthesis of (+)-trans-kumausyne and (+)- kumausallene

Journal of Organic Chemistry

Volumn 63, Issue 26, 1998, Pages 9612-9613

  Fernández De La Pradilla, Roberto ^a   Montero, Carlos ^a   Priego, Julián ^a   Martínez Cruz, Luis Alfonso ^b  

^a INSTITUTO DE QUÍMICA ORGÁNICA GENERAL   (Spain)

^b CSIC   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

ALKADIENE; ETHYLENE OXIDE DERIVATIVE; NATURAL PRODUCT; TETRAHYDROFURAN DERIVATIVE;

ARTICLE; CHEMICAL REACTION; ENANTIOMER; EPOXIDATION; REACTION ANALYSIS; RED ALGA; STEREOCHEMISTRY; SYNTHESIS;

EID: 0001060027     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo9816414     Document Type: Article

References (28)

1. Presented in part at the 12th International Conference on Organic Synthesis (ICOS-12), Venice, Italy, June 28-July 2, 1998.
2. Fernández de la Pradilla, R.; Castro, S.; Manzano, P.; Martín-Ortega, M.; Priego, J.; Viso, A.; Rodríguez, A.; Fonseca, I. J. Org. Chem. 1998, 63, 4954-4966.
3. For reviews, see: (a) Satoh, T.; Yamakawa, K. Synlett 1992, 455-468. (b) Satoh, T. Chem. Rev. 1996, 96, 3303-3325.
4. For reviews, see: (a) Satoh, T.; Yamakawa, K. Synlett 1992, 455-468. (b) Satoh, T. Chem. Rev. 1996, 96, 3303-3325.
5. Fernández de la Pradilla, R.; Manzano, P.; Priego, J.; Viso, A.; Martínez-Ripoll, M.; Rodríguez, A. Tetrahedron Lett. 1996, 37, 6793-6796.
6. For a review on the synthesis of carbohydrate derivatives from acyclic precursors, see: Ager, D. J.; East, M. B. Tetrahedron 1993, 49, 5683-5765.
7. For 1,4-additions of lithiated protected cyanohydrins to a dienyl sulfoxide, see: (a) Guillet, E.; Julia, S. Tetrahedron Lett. 1978, 37, 1155-1158. (b) Guillet, E.; Julia, S. Synth. Commun. 1981, 11, 697-708. (c) Guillet, E.; Julia, S. Synth. Commun. 1981, 11, 709-722.
8. For 1,4-additions of lithiated protected cyanohydrins to a dienyl sulfoxide, see: (a) Guillet, E.; Julia, S. Tetrahedron Lett. 1978, 37, 1155-1158. (b) Guillet, E.; Julia, S. Synth. Commun. 1981, 11, 697-708. (c) Guillet, E.; Julia, S. Synth. Commun. 1981, 11, 709-722.
9. For 1,4-additions of lithiated protected cyanohydrins to a dienyl sulfoxide, see: (a) Guillet, E.; Julia, S. Tetrahedron Lett. 1978, 37, 1155-1158. (b) Guillet, E.; Julia, S. Synth. Commun. 1981, 11, 697-708. (c) Guillet, E.; Julia, S. Synth. Commun. 1981, 11, 709-722.
10. For a review see: Harmange, J.-C.; Figadère, B. Tetrahedron: Asymmetry 1993, 4, 1711-1754.
11. Prepared in one step by the method of Craig. Craig, D.; Daniels, K.; MacKenzie, A. R. Tetrahedron 1993, 49, 11263-11304. Lithiation of Z vinyl sulfoxides yields E lithio derivatives; there are conflicting reports on the configurational stability at sulfur in this process; see: (a) Posner, G. H. In Asymmetric Reactions and Processes in Chemistry; Eliel, E. L., Otsuka, S., Eds.; ACS Symposium Series No. 185; Washington, DC, 1982; p 142. (b) Fawcett, J.; House, S.; Jenkins, P. R.; Lawrence, N. J.; Russell, D. R. J. Chem. Soc., Perkin Trans. 1 1993, 67-73.
12. Prepared in one step by the method of Craig. Craig, D.; Daniels, K.; MacKenzie, A. R. Tetrahedron 1993, 49, 11263-11304. Lithiation of Z vinyl sulfoxides yields E lithio derivatives; there are conflicting reports on the configurational stability at sulfur in this process; see: (a) Posner, G. H. In Asymmetric Reactions and Processes in Chemistry; Eliel, E. L., Otsuka, S., Eds.; ACS Symposium Series No. 185; Washington, DC, 1982; p 142. (b) Fawcett, J.; House, S.; Jenkins, P. R.; Lawrence, N. J.; Russell, D. R. J. Chem. Soc., Perkin Trans. 1 1993, 67-73.
13. Prepared in one step by the method of Craig. Craig, D.; Daniels, K.; MacKenzie, A. R. Tetrahedron 1993, 49, 11263-11304. Lithiation of Z vinyl sulfoxides yields E lithio derivatives; there are conflicting reports on the configurational stability at sulfur in this process; see: (a) Posner, G. H. In Asymmetric Reactions and Processes in Chemistry; Eliel, E. L., Otsuka, S., Eds.; ACS Symposium Series No. 185; Washington, DC, 1982; p 142. (b) Fawcett, J.; House, S.; Jenkins, P. R.; Lawrence, N. J.; Russell, D. R. J. Chem. Soc., Perkin Trans. 1 1993, 67-73.
14. All new products have been fully characterized. See the Supporting Information.
15. The reaction conditions should be strictly controlled to avoid a larger degree of overoxidation of sulfoxide 5a to sulfone 6a in the reaction medium.
16. Under these conditions a sulfonyl diene related to 3a gave a more complex mixture of inseparable sulfonyl tetrahydrofurans (62:29:9) in which 6a was the major component. This demonstrates that the sulfinyl functionality plays a crucial role in the observed stereocontrol.
17. It should be pointed out that phenyl-substituted tetrahydrofuran 5c was produced with diminished selectivity (74:14:12).
18. Hughes, D. L. Org. React. 1992, 42, 335-669.
19. For previous syntheses of trans-kumausyne, see: (a) Brown, M. J.; Harrison, T.; Overman, L. E. J. Am. Chem. Soc. 1991, 113, 5378-5384. First total synthesis of (±)-7 in 18 steps from 2-cyclopentylidenecyclopentanone. An optically enriched intermediate (84% ee) was prepared in just one additional step using (S)-O-methylprolinol as chiral controller. (b) Osumi, K.; Sugimura, H. Tetrahedron Lett. 1995, 36, 5789-5792. First enantioselective synthesis of of (-)-7 in 18 steps from L-arabinose; 12 steps are required to lactol 10, our key synthetic intermediate. (c) Martín, T.; Soler, M. A.; Betancort, J. M.; Martín, V. S. J. Org. Chem. 1997, 62, 1570-1571. Total synthesis of (+)-trans-deacetylkumausyne in 22 steps from propargyl alcohol. (d) Lee, E.; Yoo, S.-K.; Cho, Y.-S.; Cheon, H.-S.; Chong, Y. H. Tetrahedron Lett. 1997, 38, 7557-7558. Total synthesis of (-)-7 in 22 steps from D-xylose. (e) When this work was in progress Boukouvalas reported an improved synthesis of (-)-7 in 13 steps: Boukouvalas, J.; Fortier, G.; Radu, I.-I. J. Org. Chem. 1998, 62, 9916-917. This approach produces lactol 10 in seven steps from dimethyl (R)-malate.
20. For previous syntheses of trans-kumausyne, see: (a) Brown, M. J.; Harrison, T.; Overman, L. E. J. Am. Chem. Soc. 1991, 113, 5378-5384. First total synthesis of (±)-7 in 18 steps from 2-cyclopentylidenecyclopentanone. An optically enriched intermediate (84% ee) was prepared in just one additional step using (S)-O-methylprolinol as chiral controller. (b) Osumi, K.; Sugimura, H. Tetrahedron Lett. 1995, 36, 5789-5792. First enantioselective synthesis of of (-)-7 in 18 steps from L-arabinose; 12 steps are required to lactol 10, our key synthetic intermediate. (c) Martín, T.; Soler, M. A.; Betancort, J. M.; Martín, V. S. J. Org. Chem. 1997, 62, 1570-1571. Total synthesis of (+)-trans-deacetylkumausyne in 22 steps from propargyl alcohol. (d) Lee, E.; Yoo, S.-K.; Cho, Y.-S.; Cheon, H.-S.; Chong, Y. H. Tetrahedron Lett. 1997, 38, 7557-7558. Total synthesis of (-)-7 in 22 steps from D-xylose. (e) When this work was in progress Boukouvalas reported an improved synthesis of (-)-7 in 13 steps: Boukouvalas, J.; Fortier, G.; Radu, I.-I. J. Org. Chem. 1998, 62, 9916-917. This approach produces lactol 10 in seven steps from dimethyl (R)-malate.
21. For previous syntheses of trans-kumausyne, see: (a) Brown, M. J.; Harrison, T.; Overman, L. E. J. Am. Chem. Soc. 1991, 113, 5378-5384. First total synthesis of (±)-7 in 18 steps from 2-cyclopentylidenecyclopentanone. An optically enriched intermediate (84% ee) was prepared in just one additional step using (S)-O-methylprolinol as chiral controller. (b) Osumi, K.; Sugimura, H. Tetrahedron Lett. 1995, 36, 5789-5792. First enantioselective synthesis of of (-)-7 in 18 steps from L-arabinose; 12 steps are required to lactol 10, our key synthetic intermediate. (c) Martín, T.; Soler, M. A.; Betancort, J. M.; Martín, V. S. J. Org. Chem. 1997, 62, 1570-1571. Total synthesis of (+)-trans-deacetylkumausyne in 22 steps from propargyl alcohol. (d) Lee, E.; Yoo, S.-K.; Cho, Y.-S.; Cheon, H.-S.; Chong, Y. H. Tetrahedron Lett. 1997, 38, 7557-7558. Total synthesis of (-)-7 in 22 steps from D-xylose. (e) When this work was in progress Boukouvalas reported an improved synthesis of (-)-7 in 13 steps: Boukouvalas, J.; Fortier, G.; Radu, I.-I. J. Org. Chem. 1998, 62, 9916-917. This approach produces lactol 10 in seven steps from dimethyl (R)-malate.
22. For previous syntheses of trans-kumausyne, see: (a) Brown, M. J.; Harrison, T.; Overman, L. E. J. Am. Chem. Soc. 1991, 113, 5378-5384. First total synthesis of (±)-7 in 18 steps from 2-cyclopentylidenecyclopentanone. An optically enriched intermediate (84% ee) was prepared in just one additional step using (S)-O-methylprolinol as chiral controller. (b) Osumi, K.; Sugimura, H. Tetrahedron Lett. 1995, 36, 5789-5792. First enantioselective synthesis of of (-)-7 in 18 steps from L-arabinose; 12 steps are required to lactol 10, our key synthetic intermediate. (c) Martín, T.; Soler, M. A.; Betancort, J. M.; Martín, V. S. J. Org. Chem. 1997, 62, 1570-1571. Total synthesis of (+)-trans-deacetylkumausyne in 22 steps from propargyl alcohol. (d) Lee, E.; Yoo, S.-K.; Cho, Y.-S.; Cheon, H.-S.; Chong, Y. H. Tetrahedron Lett. 1997, 38, 7557-7558. Total synthesis of (-)-7 in 22 steps from D-xylose. (e) When this work was in progress Boukouvalas reported an improved synthesis of (-)-7 in 13 steps: Boukouvalas, J.; Fortier, G.; Radu, I.-I. J. Org. Chem. 1998, 62, 9916-917. This approach produces lactol 10 in seven steps from dimethyl (R)-malate.
23. For previous syntheses of trans-kumausyne, see: (a) Brown, M. J.; Harrison, T.; Overman, L. E. J. Am. Chem. Soc. 1991, 113, 5378-5384. First total synthesis of (±)-7 in 18 steps from 2-cyclopentylidenecyclopentanone. An optically enriched intermediate (84% ee) was prepared in just one additional step using (S)-O-methylprolinol as chiral controller. (b) Osumi, K.; Sugimura, H. Tetrahedron Lett. 1995, 36, 5789-5792. First enantioselective synthesis of of (-)-7 in 18 steps from L-arabinose; 12 steps are required to lactol 10, our key synthetic intermediate. (c) Martín, T.; Soler, M. A.; Betancort, J. M.; Martín, V. S. J. Org. Chem. 1997, 62, 1570-1571. Total synthesis of (+)-trans-deacetylkumausyne in 22 steps from propargyl alcohol. (d) Lee, E.; Yoo, S.-K.; Cho, Y.-S.; Cheon, H.-S.; Chong, Y. H. Tetrahedron Lett. 1997, 38, 7557-7558. Total synthesis of (-)-7 in 22 steps from D-xylose. (e) When this work was in progress Boukouvalas reported an improved synthesis of (-)-7 in 13 steps: Boukouvalas, J.; Fortier, G.; Radu, I.-I. J. Org. Chem. 1998, 62, 9916-917. This approach produces lactol 10 in seven steps from dimethyl (R)-malate.
24. Previous syntheses of kumausallene. (a) Grese, T.; Hutchinson, K.; Overman, L. E. J. Org. Chem. 1993, 58, 2468-2477. First total synthesis of (±)-8 in 21 steps from 2-cyclopentylidenecyclopentanone. Ester 9 was prepared in eight steps. (b) More recently, Lee has published an enantioselective synthesis of intermediate 9 in 16 steps from (-)-diethyl D-tartrate; see: Lee, E.; Yoo, S.-K.; Choo, H.; Song, H. Y. Tetrahedron Lett. 1998 39, 317-318.
25. Previous syntheses of kumausallene. (a) Grese, T.; Hutchinson, K.; Overman, L. E. J. Org. Chem. 1993, 58, 2468-2477. First total synthesis of (±)-8 in 21 steps from 2-cyclopentylidenecyclopentanone. Ester 9 was prepared in eight steps. (b) More recently, Lee has published an enantioselective synthesis of intermediate 9 in 16 steps from (-)-diethyl D-tartrate; see: Lee, E.; Yoo, S.-K.; Choo, H.; Song, H. Y. Tetrahedron Lett. 1998 39, 317-318.
26. The enantiomeric (1S,2R,5S)-(+)-menthyl (R)-p-toluenesulfinate is commercially available.
27. Satoh, T.; Kaneko, Y.; Izawa, T.; Yamakawa, K. Bull. Chem. Soc. Jpn. 1985, 58, 1983-1990.
28. Mereyala, H. B.; Gadikota, R.; Krishnan, R. J. Chem. Soc., Perkin Trans. 1 1997, 3567-3571.