Total syntheses of (-)-grandinolide and (-)-sapranthin by the sharpless asymmetric dihydroxylation of methyl trans-3-pentenoate: Elucidation of the stereostructure of (-)-sapranthin

Chemistry - A European Journal

Volumn 4, Issue 11, 1998, Pages 2342-2352

  Harcken, Christian ^a   Brückner, Reinhard ^a   Rank, Elisabeth ^a  

^a UNIVERSITY OF GÖTTINGEN   (Germany)

Author keywords

lactones; Asymmetric synthesis; Dihydroxylations; Rearrangements; Structure elucidation

Indexed keywords

GAMMA LACTONE DERIVATIVE; GRANDINOLIDE; SAPRANTHIN; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL STRUCTURE; CHIRALITY; ESTERIFICATION; HYDROXYLATION; STEREOCHEMISTRY; SYNTHESIS;

EID: 0031742442     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3765(19981102)4:11<2342::AID-CHEM2342>3.0.CO;2-Q     Document Type: Article

References (75)

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14. Reviews: a) B. B. Lohray, Tetrahedron: Asymmetry 1992, 3, 1317-1349; b) R. A. Johnson, K. B. Sharpless, Asymmetric Catalysis in Organic Synthesis (Ed.: I. Ojima), VCH, New York, 1993, 227-272; c) H. C. Kolb, M. S. Van Nieuwenhze, K. B. Sharpless, Chem. Rev. 1994, 94, 2483-2547; d) G. Poli, C. Scolastico in Methoden Org. Chem. (Houben-Weyl) 4th ed. 1952, Vol. E21e (Eds.: G. Helmchen, R. W. Hoffmann, J. Mulzer, E. Schaumann), Thieme, Stuttgart, 1995, pp. 4547-4598.
15. Reviews: a) B. B. Lohray, Tetrahedron: Asymmetry 1992, 3, 1317-1349; b) R. A. Johnson, K. B. Sharpless, Asymmetric Catalysis in Organic Synthesis (Ed.: I. Ojima), VCH, New York, 1993, 227-272; c) H. C. Kolb, M. S. Van Nieuwenhze, K. B. Sharpless, Chem. Rev. 1994, 94, 2483-2547; d) G. Poli, C. Scolastico in Methoden Org. Chem. (Houben-Weyl) 4th ed. 1952, Vol. E21e (Eds.: G. Helmchen, R. W. Hoffmann, J. Mulzer, E. Schaumann), Thieme, Stuttgart, 1995, pp. 4547-4598.
16. Z.-M. Wang, X.-L. Zhang, K. B. Sharpless, S. C. Sinha, A. Sinha-Bagchi, E. Keinan, Tetrahedron Lett. 1992, 33, 6407-6410; Y. Miyazaki, H. Hotta, F. Sato, Tetrahedron Lett. 1994, 35, 4389-4392.
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18. Preparation of AD mixes: K. B. Sharpless, W. Amherg, Y. L. Bennani, G. A. Crispino, J. Hartung, K.-S. Jeong, H. L. Kwong, K. Morikawa, Z. M. Wang, D. Xu, X. L. Zhang, J. Org. Chem. 1992, 57, 2768-2771.
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23. Previous preparation of this compound: S. Y. Chen, M. M. Joullié, J. Org. Chem. 1984, 49, 2168-2174.
24. ADs of disubstituted olefins trans-Me-CH=CH - R were reported to show 72% ee in the cases of 2-butene (unpublished results in ref. [4c]) and trans-4,5-diphenyl-2-(trans-3-pentenyl)-1,3-dioxolane (A. Sobti, G. A. Sulikowski, Tetrahedron Lett. 1995, 36, 4193-4196), 73% ee in the case of 1-phenylpent-3-en-1-yne (K.-S. Jeong, P. Sjö, K. B. Sharpless, Tetrahedron Lett. 1992, 33, 3833-3836), and 95% ee in the cases of 1-chloro-2-butene (K. P. M. Vanhessche, Z.-M. Wang, K. B. Sharpless, Tetrahedron Lett. 1994, 35, 3469-3472) or 4,4-dimethyl-2-pentene (unpublished results in ref. [4c]).
25. ADs of disubstituted olefins trans-Me-CH=CH - R were reported to show 72% ee in the cases of 2-butene (unpublished results in ref. [4c]) and trans-4,5-diphenyl-2-(trans-3-pentenyl)-1,3-dioxolane (A. Sobti, G. A. Sulikowski, Tetrahedron Lett. 1995, 36, 4193-4196), 73% ee in the case of 1-phenylpent-3-en-1-yne (K.-S. Jeong, P. Sjö, K. B. Sharpless, Tetrahedron Lett. 1992, 33, 3833-3836), and 95% ee in the cases of 1-chloro-2-butene (K. P. M. Vanhessche, Z.-M. Wang, K. B. Sharpless, Tetrahedron Lett. 1994, 35, 3469-3472) or 4,4-dimethyl-2-pentene (unpublished results in ref. [4c]).
26. ADs of disubstituted olefins trans-Me-CH=CH - R were reported to show 72% ee in the cases of 2-butene (unpublished results in ref. [4c]) and trans-4,5-diphenyl-2-(trans-3-pentenyl)-1,3-dioxolane (A. Sobti, G. A. Sulikowski, Tetrahedron Lett. 1995, 36, 4193-4196), 73% ee in the case of 1-phenylpent-3-en-1-yne (K.-S. Jeong, P. Sjö, K. B. Sharpless, Tetrahedron Lett. 1992, 33, 3833-3836), and 95% ee in the cases of 1-chloro-2-butene (K. P. M. Vanhessche, Z.-M. Wang, K. B. Sharpless, Tetrahedron Lett. 1994, 35, 3469-3472) or 4,4-dimethyl-2-pentene (unpublished results in ref. [4c]).
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33. The enantiomer of 9 was synthesized by: a) S. Aburaki, N. Konishi, M. Kinoshita, Bull. Chem. Soc. Jpn. 1975, 48, 1254-1259; b) J. Mulzer, T. Schulze, A. Strecker, W. Denzer, J. Org. Chem. 1988, 53, 4098-4103; and c) M. P. Sibi, J. Lu, C. L. Talbacka, J. Org. Chem. 1996, 61, 7848-7855; and d) racemic 9 by C. Mukai, O. Kataoka, M. Hanaoka, J. Org. Chem. 1993, 58, 2946-2952.
34. The enantiomer of 9 was synthesized by: a) S. Aburaki, N. Konishi, M. Kinoshita, Bull. Chem. Soc. Jpn. 1975, 48, 1254-1259; b) J. Mulzer, T. Schulze, A. Strecker, W. Denzer, J. Org. Chem. 1988, 53, 4098-4103; and c) M. P. Sibi, J. Lu, C. L. Talbacka, J. Org. Chem. 1996, 61, 7848-7855; and d) racemic 9 by C. Mukai, O. Kataoka, M. Hanaoka, J. Org. Chem. 1993, 58, 2946-2952.
35. The enantiomer of 9 was synthesized by: a) S. Aburaki, N. Konishi, M. Kinoshita, Bull. Chem. Soc. Jpn. 1975, 48, 1254-1259; b) J. Mulzer, T. Schulze, A. Strecker, W. Denzer, J. Org. Chem. 1988, 53, 4098-4103; and c) M. P. Sibi, J. Lu, C. L. Talbacka, J. Org. Chem. 1996, 61, 7848-7855; and d) racemic 9 by C. Mukai, O. Kataoka, M. Hanaoka, J. Org. Chem. 1993, 58, 2946-2952.
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50. P. Wipf, in Comprehensive Organic Synthesis, Vol. 5 (Eds.: B. M. Trost. I. Fleming) [Combining C-C π-Bonds (Ed.: L. A Raquette)], Pergamon, Oxford. 1991, pp. 827-873; S. Pereira, M. Srebnik, Aldrichimica Acta 1993, 26, 17-29; H. Frauenrath, in Methoden Org. Chem. (Houben-Weyl) 4th ed. 1952-, Vol. E21e (Eds.: G. Helmchen, R. W. Hoffmann, J. Mulzer, E. Schaumann), Thieme, Stuttgart, 1995, pp. 3301-3547.
51. P. Wipf, in Comprehensive Organic Synthesis, Vol. 5 (Eds.: B. M. Trost. I. Fleming) [Combining C-C π-Bonds (Ed.: L. A Raquette)], Pergamon, Oxford. 1991, pp. 827-873; S. Pereira, M. Srebnik, Aldrichimica Acta 1993, 26, 17-29; H. Frauenrath, in Methoden Org. Chem. (Houben-Weyl) 4th ed. 1952-, Vol. E21e (Eds.: G. Helmchen, R. W. Hoffmann, J. Mulzer, E. Schaumann), Thieme, Stuttgart, 1995, pp. 3301-3547.
52. Directly after submitting our manuscript a report of similar consecutive Claisen - Ireland and Cope rearrangements appeared: S. Gil, M. A. Lázaro, M. Parra, E. Breitmaier, R. Mestres, Synlett 1998, 70-72.
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57. G. H. Jeffery, A. I. Vogel, J. Chem. Soc. 1948, 658-673.
58. Procedure: K. Mori, M. Amaike, H. Watanabe, Liebigs Ann. Chem 1993, 1287-1294.
59. The ethyl analogue of methyl ester 26 was obtained by J. L. Herrmann, G. R. Kieczykowski, R. H. Schlessinger, Tetrahedron Lett. 1973, 2433-2436 from ethyl crotonate, LDA, and allyl bromide; the presence of 1.1 equivalents of HMPA (carcinogenic) was required because otherwise (we confirmed this) only ethyl 3-(diisopropylamino)butyrate is obtained. The analogous allylation in the presence of 1.0 equivalents of DMPU still provided ethyl 3-(diisopropylamino)butyrate as the major product and no more than 30% of the ethyl ester analogue of 26. Similar allylations in a 1:1 mixture of THF and DMPU gave the latter compound not at all, 40% ethyl 2,2-diallyl-3-butenoate and unreacted ethyl crotonate.
60. We did not combine the Claisen - Ireland and the Cope rearrangements of Scheme 5 in a tandem reaction even if tandem Claisen/Cope rearrangements are in principle known: F. E. Ziegler, in Comprehensive Organic Synthesis, Vol. 5 (Eds.: B. M. Trost, I. Fleming) [Combining C-C π-Bonds(Ed.: L. A Paquette)], Pergamon, Oxford, 1991, pp. 875-898.
61. Other syntheses of dienol 30: X. Beebe, C. L. Chiappari, M. J. Kurth, N. E. Schore, J. Org. Chem. 1993, 58, 7320-7321; S. Araki, H. Usui, M. Kato, Y. Butsugan, J. Am. Chem. Soc. 1996, 118, 4699-4700. A one-step synthesis from butadienoxide (Y. Naruta, K. Maruyama, Chem. Lett. 1987, 963-966) gave 82% 30 and 19% 2-vinyl-3-buten-1-ol.
62. Other syntheses of dienol 30: X. Beebe, C. L. Chiappari, M. J. Kurth, N. E. Schore, J. Org. Chem. 1993, 58, 7320-7321; S. Araki, H. Usui, M. Kato, Y. Butsugan, J. Am. Chem. Soc. 1996, 118, 4699-4700. A one-step synthesis from butadienoxide (Y. Naruta, K. Maruyama, Chem. Lett. 1987, 963-966) gave 82% 30 and 19% 2-vinyl-3-buten-1-ol.
63. Other syntheses of dienol 30: X. Beebe, C. L. Chiappari, M. J. Kurth, N. E. Schore, J. Org. Chem. 1993, 58, 7320-7321; S. Araki, H. Usui, M. Kato, Y. Butsugan, J. Am. Chem. Soc. 1996, 118, 4699-4700. A one-step synthesis from butadienoxide (Y. Naruta, K. Maruyama, Chem. Lett. 1987, 963-966) gave 82% 30 and 19% 2-vinyl-3-buten-1-ol.
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72. methine-O oxidation required for reaching the target structure 41.
73. Method: I. Fleming, R. Henning, D. C. Parker, H. E. Plant, P. E. J. Sanderson, J. Chem. Soc. Perkin Trans. I 1995, 317-337.
74. 1H NMR spectrum of (-)sapranthin shows a 4-H signal which is identical to the 4-H signal of synthetic 41 (ref. [48]).
75. P. G. Waterman, personal communication.