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Volumn 5, Issue 6, 2003, Pages 913-916

Synthesis of an F-H gambierol subunit using a C-glycoside-centered strategy

Author keywords

[No Author keywords available]

Indexed keywords

ENOL ETHER; ETHER DERIVATIVE; GAMBIEROL; GLYCOSIDE; UNCLASSIFIED DRUG; CIGUATOXIN; DYES, REAGENTS, INDICATORS, MARKERS AND BUFFERS; POLYCYCLIC HYDROCARBON;

EID: 0038615829     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol034100w     Document Type: Article
Times cited : (56)

References (44)
  • 10
    • 0002521312 scopus 로고    scopus 로고
    • Bertozzi, C., Wang, P. G., Eds.; Marcel Dekker: New York
    • For a recent monograph on C-glycoside synthesis, see: Postema, M. H. D. In Glycochemistry Principles, Synthesis and Applications; Bertozzi, C., Wang, P. G., Eds.; Marcel Dekker: New York, 2000; pp 77-131.
    • (2000) Glycochemistry Principles, Synthesis and Applications , pp. 77-131
    • Postema, M.H.D.1
  • 14
    • 0037175485 scopus 로고    scopus 로고
    • Among the more challenging structural features of gambierol are the C(7), C(11), C(21), and C(23) stereocenters. These centers contain angular methyl groups oriented in a 1,3-disposition to one another and, for our approach, require the addition of a carbon nucleophile to the more substituted end of a trisubstituted glycal anhydride. For synthetic work by others toward these centers, see refs 3 and 4 and: Suzuki, K.; Matsukura, H.; Matsuo, G.; Koshino, H.; Nakata, T. Tetrahedron Lett. 2002, 43, 8653.
    • (2002) Tetrahedron Lett. , vol.43 , pp. 8653
    • Suzuki, K.1    Matsukura, H.2    Matsuo, G.3    Koshino, H.4    Nakata, T.5
  • 19
    • 0029978637 scopus 로고    scopus 로고
    • To obtain reproducible yields on a large scale, we used Messeguer's "acetone-free" conditions. The use of this protocol allowed us to avoid the concentration of the epoxide. See the Experimental Section and: Ferrer, M.; Gibert, M.; Sánchez-Baeza, F.; Messeguer, A. Tetrahedron Lett. 1996, 37, 3585.
    • (1996) Tetrahedron Lett. , vol.37 , pp. 3585
    • Ferrer, M.1    Gibert, M.2    Sánchez-Baeza, F.3    Messeguer, A.4
  • 20
    • 0141485878 scopus 로고    scopus 로고
    • note
    • Our previous work with similarly substituted epoxides had resulted in poor diastereoselectivity and/or low yields. The major products from these reactions were generally rationalized as coming from the formation of intermediate oxocarbenium ions. See refs 6 and 8.
  • 21
    • 0141597527 scopus 로고    scopus 로고
    • note
    • We have also coupled Al nucleophiles with trisubstituted glycal anhydrides. See refs 6b and 6c.
  • 22
    • 0000498386 scopus 로고
    • For selected examples of enol ether-olefin RCM, see: (a) Fujimura, O.; Fu, G. C.; Grubbs, R. H. J. Org. Chem. 1994, 59, 4029. (b) Clark, J. S.; Kettle, J. G. Tetrahedron Lett. 1997, 38, 123. (c) Postema, M. H. D. J. Org. Chem. 1999, 64, 1770. (d) Clark, J. S.; Hamelin, O. Angew. Chem., Int. Ed. 2000, 39, 372. (e) Chatterjee, A. K.; Morgan, J. P.; Scholl, M.; Grubbs, R. H. J. Am. Chem. Soc. 2000, 122, 3783. (f) Rainier, J. D.; Cox, J. M.; Allwein, S. P. Tetrahedron Lett. 2001, 42, 179.
    • (1994) J. Org. Chem. , vol.59 , pp. 4029
    • Fujimura, O.1    Fu, G.C.2    Grubbs, R.H.3
  • 23
    • 0031031774 scopus 로고    scopus 로고
    • For selected examples of enol ether-olefin RCM, see: (a) Fujimura, O.; Fu, G. C.; Grubbs, R. H. J. Org. Chem. 1994, 59, 4029. (b) Clark, J. S.; Kettle, J. G. Tetrahedron Lett. 1997, 38, 123. (c) Postema, M. H. D. J. Org. Chem. 1999, 64, 1770. (d) Clark, J. S.; Hamelin, O. Angew. Chem., Int. Ed. 2000, 39, 372. (e) Chatterjee, A. K.; Morgan, J. P.; Scholl, M.; Grubbs, R. H. J. Am. Chem. Soc. 2000, 122, 3783. (f) Rainier, J. D.; Cox, J. M.; Allwein, S. P. Tetrahedron Lett. 2001, 42, 179.
    • (1997) Tetrahedron Lett. , vol.38 , pp. 123
    • Clark, J.S.1    Kettle, J.G.2
  • 24
    • 0033583130 scopus 로고    scopus 로고
    • For selected examples of enol ether-olefin RCM, see: (a) Fujimura, O.; Fu, G. C.; Grubbs, R. H. J. Org. Chem. 1994, 59, 4029. (b) Clark, J. S.; Kettle, J. G. Tetrahedron Lett. 1997, 38, 123. (c) Postema, M. H. D. J. Org. Chem. 1999, 64, 1770. (d) Clark, J. S.; Hamelin, O. Angew. Chem., Int. Ed. 2000, 39, 372. (e) Chatterjee, A. K.; Morgan, J. P.; Scholl, M.; Grubbs, R. H. J. Am. Chem. Soc. 2000, 122, 3783. (f) Rainier, J. D.; Cox, J. M.; Allwein, S. P. Tetrahedron Lett. 2001, 42, 179.
    • (1999) J. Org. Chem. , vol.64 , pp. 1770
    • Postema, M.H.D.1
  • 25
    • 0034677109 scopus 로고    scopus 로고
    • For selected examples of enol ether-olefin RCM, see: (a) Fujimura, O.; Fu, G. C.; Grubbs, R. H. J. Org. Chem. 1994, 59, 4029. (b) Clark, J. S.; Kettle, J. G. Tetrahedron Lett. 1997, 38, 123. (c) Postema, M. H. D. J. Org. Chem. 1999, 64, 1770. (d) Clark, J. S.; Hamelin, O. Angew. Chem., Int. Ed. 2000, 39, 372. (e) Chatterjee, A. K.; Morgan, J. P.; Scholl, M.; Grubbs, R. H. J. Am. Chem. Soc. 2000, 122, 3783. (f) Rainier, J. D.; Cox, J. M.; Allwein, S. P. Tetrahedron Lett. 2001, 42, 179.
    • (2000) Angew. Chem. Int. Ed. , vol.39 , pp. 372
    • Clark, J.S.1    Hamelin, O.2
  • 26
    • 0034685462 scopus 로고    scopus 로고
    • For selected examples of enol ether-olefin RCM, see: (a) Fujimura, O.; Fu, G. C.; Grubbs, R. H. J. Org. Chem. 1994, 59, 4029. (b) Clark, J. S.; Kettle, J. G. Tetrahedron Lett. 1997, 38, 123. (c) Postema, M. H. D. J. Org. Chem. 1999, 64, 1770. (d) Clark, J. S.; Hamelin, O. Angew. Chem., Int. Ed. 2000, 39, 372. (e) Chatterjee, A. K.; Morgan, J. P.; Scholl, M.; Grubbs, R. H. J. Am. Chem. Soc. 2000, 122, 3783. (f) Rainier, J. D.; Cox, J. M.; Allwein, S. P. Tetrahedron Lett. 2001, 42, 179.
    • (2000) J. Am. Chem. Soc. , vol.122 , pp. 3783
    • Chatterjee, A.K.1    Morgan, J.P.2    Scholl, M.3    Grubbs, R.H.4
  • 27
    • 0035825039 scopus 로고    scopus 로고
    • For selected examples of enol ether-olefin RCM, see: (a) Fujimura, O.; Fu, G. C.; Grubbs, R. H. J. Org. Chem. 1994, 59, 4029. (b) Clark, J. S.; Kettle, J. G. Tetrahedron Lett. 1997, 38, 123. (c) Postema, M. H. D. J. Org. Chem. 1999, 64, 1770. (d) Clark, J. S.; Hamelin, O. Angew. Chem., Int. Ed. 2000, 39, 372. (e) Chatterjee, A. K.; Morgan, J. P.; Scholl, M.; Grubbs, R. H. J. Am. Chem. Soc. 2000, 122, 3783. (f) Rainier, J. D.; Cox, J. M.; Allwein, S. P. Tetrahedron Lett. 2001, 42, 179.
    • (2001) Tetrahedron Lett. , vol.42 , pp. 179
    • Rainier, J.D.1    Cox, J.M.2    Allwein, S.P.3
  • 28
    • 0141709214 scopus 로고    scopus 로고
    • Ph.D. Dissertation, The University of Arizona, Tucson, Arizona
    • To the best of our knowledge, the only other example of the formation of a tetrasubstituted enol ether using metathesis also came from our laboratory. See: Cox, J. M. Ph.D. Dissertation, The University of Arizona, Tucson, Arizona, 2002.
    • (2002)
    • Cox, J.M.1
  • 30
    • 0141597526 scopus 로고    scopus 로고
    • note
    • Other enol ether-forming protocols (Tebbe, Petasis) were even less successful in our hands.
  • 34
    • 0000559010 scopus 로고    scopus 로고
    • We believe that there could be two reasons for the need for elevated temperatures: (1) the inherent difficulty associated with generating tetrasubstituted enol ethers; (2) the reaction may be proceeding through a relatively unreactive Fischer carbene intermediate prior to cyclization. For an excellent study on the formation and reactivity of Fischer carbenes from enol ethers and 14, see: Louie, J.; Grubbs, R. H. Organometallics 2002, 21, 2153.
    • (2002) Organometallics , vol.21 , pp. 2153
    • Louie, J.1    Grubbs, R.H.2
  • 36
    • 0141485876 scopus 로고    scopus 로고
    • note
    • Attempts to selectively remove the TBDPS group from 10 were unsuccessful.
  • 38
    • 0141820528 scopus 로고    scopus 로고
    • note
    • We also attempted to cyclize 17 using Schrock's catalyst 13 without success.
  • 41
    • 0141485877 scopus 로고    scopus 로고
    • note
    • Minor product from this coupling is diastereomeric at C(20). We believe that this material comes from the direct reduction of 19.
  • 42
    • 0141820527 scopus 로고    scopus 로고
    • note
    • Another possibility would involve an RCM sequence. We have previously demonstrated the generation of oxepenes using RCM; see ref 6c.


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