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Volumn 9, Issue 16, 2007, Pages 2989-2992

Synthesis of (-)-agelastatin a by [3.3] sigmatropic rearrangement of allyl cyanate

Author keywords

[No Author keywords available]

Indexed keywords

AGELASTATIN A; ALKALOID; ALLYL COMPOUND; ARABINITOL; CYANIC ACID DERIVATIVE; OXAZOLIDINONE DERIVATIVE; SUGAR ALCOHOL; UNCLASSIFIED DRUG;

EID: 34547953030     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol0709735     Document Type: Article
Times cited : (74)

References (40)
  • 10
    • 0027170397 scopus 로고    scopus 로고
    • For the isolation and biological activities of (-)-agelastatin A: (a) D'Ambrosio, M.; Guerriero, A.; Debitus, C.; Ribes, O.; Pusset, J.; Leroy, S.; Pietra, F. J. Chem. Soc., Chem. Commun. 1993, 1305.
    • For the isolation and biological activities of (-)-agelastatin A: (a) D'Ambrosio, M.; Guerriero, A.; Debitus, C.; Ribes, O.; Pusset, J.; Leroy, S.; Pietra, F. J. Chem. Soc., Chem. Commun. 1993, 1305.
  • 22
    • 34547943393 scopus 로고    scopus 로고
    • Benzoate 11 was readily prepared from commercially available L-arabitol in 80% yield over two steps through acetonidation followed by protection of the resultant primary alcohol as benzoate. See, Bukhari, M. S.; Foster, A. B.; Lehmann, J.; Webber, J. M.; Westwood, J. H. J. Chem. Soc. 1963, 2291.
    • Benzoate 11 was readily prepared from commercially available L-arabitol in 80% yield over two steps through acetonidation followed by protection of the resultant primary alcohol as benzoate. See, Bukhari, M. S.; Foster, A. B.; Lehmann, J.; Webber, J. M.; Westwood, J. H. J. Chem. Soc. 1963, 2291.
  • 28
    • 37049087800 scopus 로고    scopus 로고
    • This dehydration condition was first reported as a synthetic method for the preparation of isonitrile from formamide. See: Ichikawa, Y. J. Chem. Soc, Perkin Trans. 1 1992, 2135
    • This dehydration condition was first reported as a synthetic method for the preparation of isonitrile from formamide. See: Ichikawa, Y. J. Chem. Soc., Perkin Trans. 1 1992, 2135.
  • 29
    • 33748734782 scopus 로고    scopus 로고
    • Addition of tributyltin alkoxide enhanced the yields of this in situ transformation of isocyanate into the corresponding carbamate. See: (a) Ichikawa, Y, Osada, M, Ohtani, I, Isobe, M. J. Chem. Soc, Perkin Trans. 1 1997, 1449
    • Addition of tributyltin alkoxide enhanced the yields of this in situ transformation of isocyanate into the corresponding carbamate. See: (a) Ichikawa, Y.; Osada, M.; Ohtani, I.; Isobe, M. J. Chem. Soc., Perkin Trans. 1 1997, 1449.
  • 32
    • 34547939612 scopus 로고    scopus 로고
    • Our initial route focused on exploiting the fully protected 1,6-diene i as a substrate for RCM, because oxazolidinone ring was expected to induce turn-structure on the diene to facilitate the ring- closure process; in fact, cyclopentene ii was obtained in good yields. Unfortunately, we encountered difficulty associated with the manipulation of the carbamate group in ii, which revised our protecting group strategy. As a result, 8 was chosen as a substrate for RCM. Equation presented
    • Our initial route focused on exploiting the fully protected 1,6-diene i as a substrate for RCM, because oxazolidinone ring was expected to induce turn-structure on the diene to facilitate the ring- closure process; in fact, cyclopentene ii was obtained in good yields. Unfortunately, we encountered difficulty associated with the manipulation of the carbamate group in ii, which revised our protecting group strategy. As a result, 8 was chosen as a substrate for RCM. Equation presented.
  • 35
    • 41649120463 scopus 로고    scopus 로고
    • Similar strategy using bromopyrrole was noted in the previous synthesis of Hale, which was rationalized and modified in our route. Hale, K. J.; Domostoj, M. M.; El-Tanami, M.; Campbell, F. C.; Mason, C. K. Total Synthesis and Mechanism of Action Studies on the Antitumor Alkaloid, (-)-agelastatin A. In Strategies and Tactics in Organic Synthesis; Harmata, M., Ed.; Elsevier: 2005; pp 352-394. See also ref 10b and Supporting Information.
    • Similar strategy using bromopyrrole was noted in the previous synthesis of Hale, which was rationalized and modified in our route. Hale, K. J.; Domostoj, M. M.; El-Tanami, M.; Campbell, F. C.; Mason, C. K. Total Synthesis and Mechanism of Action Studies on the Antitumor Alkaloid, (-)-agelastatin A. In Strategies and Tactics in Organic Synthesis; Harmata, M., Ed.; Elsevier: 2005; pp 352-394. See also ref 10b and Supporting Information.
  • 40
    • 34547954682 scopus 로고    scopus 로고
    • Commercially available methyl isocyanate was dissolved in THF and then used as a THF-solution, which was titrated by the reaction with excess benzylamine and isolation of the produced methyl benzyl urea. We thank Prof. Weinreb, Dr. Stien, and Prof. Davis for informing us of the source of methyl isocyanate see ref 8a and 11
    • Commercially available methyl isocyanate was dissolved in THF and then used as a THF-solution, which was titrated by the reaction with excess benzylamine and isolation of the produced methyl benzyl urea. We thank Prof. Weinreb, Dr. Stien, and Prof. Davis for informing us of the source of methyl isocyanate (see ref 8a and 11).


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.