The phenylsulfonyl group as an endo stereochemical controller in intramolecular Pauson-Khand reactions of 3-oxygenated 1,6-enynes

Angewandte Chemie - International Edition

Volumn 39, Issue 16, 2000, Pages 2906-2909

  Adrio, Javier ^a   Rodríguez Rivero, Marta ^a   Carretero, Juan C ^a  

^a UNIVERSIDAD AUTÓNOMA DE MADRID   (Spain)

Author keywords

Asymmetric synthesis; Cyclizations; Enynes; Pauson Khand reactions; Sulfones

Indexed keywords

1 SULFINYL 1,6 ENYNE; PHENYL GROUP; SULFONE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL REACTION; CYCLIZATION; PROTON NUCLEAR MAGNETIC RESONANCE; RACEMIC MIXTURE; STEREOCHEMISTRY;

EID: 0040778402     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/1521-3773(20000818)39:16<2906::AID-ANIE2906>3.0.CO;2-8     Document Type: Article

References (46)

1. Recent reviews: a) Y. K. Chung, Coord. Chem. Rev. 1999, 188, 297;
2. b) O. Geis, H.-G. Schmalz, Angew. Chem. 1998, 110, 955: Angew. Chem. Int. Ed. 1998, 37, 911;
3. b) O. Geis, H.-G. Schmalz, Angew. Chem. 1998, 110, 955: Angew. Chem. Int. Ed. 1998, 37, 911;
4. c) J. Marco-Contelles, S. T. Ingate, Org. Prep. Proced. Int. 1998, 30, 121;
5. d) N. E. Schore in Comprehensive Organometallic Chemistry II (Eds.: E. W. Abel, F. G. A. Stone, G. Wilkinson), Elsevier, New York, 1995, Vol. 12, p. 703;
6. d) N. E. Schore, Org. React. 1991, 40, 1.
7. The exo selectivity of the intramolecular PK reaction of allylic substituted 1,6-enynes has been explained by invoking steric repulsion between the endo allylic group and the substituent at the alkyne terminus in the cis-cobaltacycle intermediate:
8. a) P. Magnus, D. P. Becker, J. Am. Chem. Soc. 1987, 109, 7495;
9. b) P. Magnus, L. M. Principe, M. J. Slater, J. Org. Chem. 1987, 52, 1483;
10. c) P. Magnus, L. M. Principe, Tetrahedron Lett. 1985, 26, 4851;
11. d) P. Magnus, C. Exon, P. Albaugh-Robertson, Tetrahedron 1985, 41, 5861.
12. For other examples of exo selectivity in PK cyclizations of enynes substituted at allylic or propargylic positions, see a) C. Mukai, J. S. Kim, M. Uchiyama, S. Sakamoto, M. Hanoka, J. Chem. Soc. Perkin Trans I 1998, 2903;
13. b) C. Mukai, M. Uchiyama, S. Sakamoto, M. Hanaoka, Tetrahedron Lett. 1995, 36, 5761;
14. c) N. Jeong, S. Hwang, Y. Lee, Y. K. Chung, J. Am. Chem. Soc. 1994, 116, 3159;
15. d) Y. K. Chung, B. Y. Lee, N. Jeong, M. Hudecek, P. L. Pauson, Organometallics 1993, 12, 220;
16. e) N. Jeong, B. Y. Lee, S. M. Lee, Y. K. Chung, S.-G. Lee, Tetrahedron Lett. 1993, 34, 4023;
17. f) S. Yoo, S. H. Lee, N. Jeong, I. Cho, Tetrahedron Lett. 1993, 34, 3425.
18. g) W. R. Roush, J. C. Park, Tetrahedron Lett. 1991, 32, 6285:
19. h) N. Jeong, S. Yoo, S. J. Lee, S. H. Lee, Y. K. Chung, Tetrahedron Lett. 1991, 32, 2137:
20. J. Mulzer, K.-D. Graske, B. Kirste, Liebigs Ann. Chem. 1988, 891.
21. One of the most important limitations of the cyclopentenone synthesis by the PK reaction is that in the reaction of alkyne dicobalt hexacarbonyl complexes with alkenes bearing electron-withdrawing groups (for example, ketone, ester, or cyano), after the olefin insertion step leading to the cobaltacycle intermediate, the reaction proceeds preferentially by β-H elimination rather than by carbonyl insertion, furnishing finally 1,3-dienes instead of cyclopentenones; see a) W. A. Smit, A. S. Gybin, A. S. Shashkov, Y. T. Strychkov, L. G. Kizmina, G. S. Mikaelian, R. Caple, E. D. Swanson, Tetrahedron Lett. 1986, 27, 1241;
22. b) P. L. Pauson, Tetrahedron 1985, 41, 5855;
23. c) I. U. Khand, P. L. Pauson, J. Chem. Soc. Chem. Commun. 1974, 379. Only some specific alkynyl enones led to cyclopentenones in cobalt-catalyzed PK reactions: A. L. Veretenov, W. A. Smit, L. G. Vorontsova, M. G. Kurella, R. Caple, A. S. Gibin, Tetrahedron Lett. 1991, 32, 2109. See also M. Costa, A. Mor, Tetrahedron Lett. 1995, 36, 2867.
24. c) I. U. Khand, P. L. Pauson, J. Chem. Soc. Chem. Commun. 1974, 379. Only some specific alkynyl enones led to cyclopentenones in cobalt-catalyzed PK reactions: A. L. Veretenov, W. A. Smit, L. G. Vorontsova, M. G. Kurella, R. Caple, A. S. Gibin, Tetrahedron Lett. 1991, 32, 2109. See also M. Costa, A. Mor, Tetrahedron Lett. 1995, 36, 2867.
25. c) I. U. Khand, P. L. Pauson, J. Chem. Soc. Chem. Commun. 1974, 379. Only some specific alkynyl enones led to cyclopentenones in cobalt-catalyzed PK reactions: A. L. Veretenov, W. A. Smit, L. G. Vorontsova, M. G. Kurella, R. Caple, A. S. Gibin, Tetrahedron Lett. 1991, 32, 2109. See also M. Costa, A. Mor, Tetrahedron Lett. 1995, 36, 2867.
26. J. Adrio, J. C. Carretero, J. Am. Chem. Soc: 1999, 121, 7411.
27. Vinyl sulfones had never been successfully used in PK reactions. As a related reported precedent, the treatment of divinyl sulfone with alkyne dicobalt complexes did not give the cyclopentenone PK product (I. U. Khand, P. L. Pauson, Heterocycles 1978, 11, 59) in accordance with the accepted behavior of alkenes with electron-withdrawing substituents (see ref. [4]).
28. To the best of our knowledge, the only reported case of endo selectivity in a PK reaction of an allylic substituted 1,6-enyne concerns a specific 3,4-disubstituted enyne: J. A. Casalnuovo, R. W. Scott, E. A. Harwood, N. E. Schore, Tetrahedron Lett. 1994, 35, 1153. Similarly, for a study of the endolexo selectivity in 3,4-disubstituted-1,7-enynes, see C. Mukai, J. S. Kim, H. Sonobe, M. Hanaoka, J. Org. Chem. 1999, 64, 6822.
29. To the best of our knowledge, the only reported case of endo selectivity in a PK reaction of an allylic substituted 1,6-enyne concerns a specific 3,4-disubstituted enyne: J. A. Casalnuovo, R. W. Scott, E. A. Harwood, N. E. Schore, Tetrahedron Lett. 1994, 35, 1153. Similarly, for a study of the endolexo selectivity in 3,4-disubstituted-1,7-enynes, see C. Mukai, J. S. Kim, H. Sonobe, M. Hanaoka, J. Org. Chem. 1999, 64, 6822.
30. a) B. M. Trost, T. A. Greese, J. Org. Chem. 1991, 56, 3189;
31. b) E. Domínguez, J. C. Carretero, Tetrahedron 1990, 46, 7197.
32. 3N 200 mol% in benzene at RT; 81 and 75% yield, respectively).
33. 3CN, 80°C) of the dicobalt complexes of the enynes 1 and 3.
34. The combination TMANO/molecular sieves has been recently reported as an efficient promoter in PK reactions: L. Pérez-Serrano, L. Casarrubios, G. Domínguez, J. Pérez-Castells, Org. Lett. 1999, 1, 1187.
35. 2, RT). A very low yield of PK products 9a (25% yield, endolexo = 85/15) was obtained when the reaction was performed in the presence of TMANO and molecular sieves. In this case, instead of the PK cyclopentenone, the main product was the corresponding exocyclic 1,3-diene (see ref. [4]).
36. 6 is significantly more deshielded in the endo isomer than in the exo isomer (see below), in accordance with the strong deshielding effect of the phenylsulfonyl group on the hydrogen atom in the 1,3-parallel arrangement. Additionally, these stereochemical assignments have been confirmed by NOESY experiments on the pairs of isomers endol exo 9b and endolexo 13c. matrix presented
37. Crystallographic data (excluding structure factors) for the structures reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-141942. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road. Cambridge CB2 1EZ, UK (fax: (+44) 1223-336-033; e-mail: deposit@ccdc.cam.ac.uk).
38. Recent examples: S. Fonquerna, R. Rios, A. Moyano, M. A. Pericàs, A. Riera, Eur. J. Org. Chem. 1999, 3459, and references therein.
39. For instance, see a) P. M. Breczinski, A. Stumpf, H. Hope, M. E. Krafft, J. A. Casalnuovo, N. E. Schore, Tetrahedron 1999, 55, 6797;
40. b) J. Castro, A. Moyano, M. A. Pericàs, A. Riera, Tetrahedron 1995, 51, 6541.
41. a) J. C. Carretero, R. Gómez Arrayás, J. Org. Chem. 1998, 63, 2993;
42. b) J. Adrio, J. C. Carretero, R. Gómez Arrayás, Synlett 1996, 640.
43. Similar conformational preferences have been reported for γ-oxygenated αβ-unsaturated esters, see: c) B. W. Gung, M. B. Francis, Tetrahedron Lett. 1995, 36, 2579;
44. d) B. W. Gung, M. B. Francis, J. Org. Chem. 1993, 58, 6177.
45. In all the studied cases, only the R enantiomer of the (±)-(E)-γy-hydroxy-αβ-unsaturated sulfone was acetylated (J. C. Carretero, E. Domínguez, J. Org. Chem. 1992, 57, 3867).
46. 3).