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Volumn 48, Issue 19, 2009, Pages 3462-3465

First stereoselective total synthesis of FD-594 aglycon

Author keywords

Antibiotics; Atropisomerism; Natural product synthesis; Samarium; Total synthesis

Indexed keywords

ATROPISOMERISM; CHIRAL NUCLEOPHILES; FUNCTIONALIZED; NATURAL PRODUCT SYNTHESIS; PINACOLS; STEREO-SELECTIVE; TOTAL SYNTHESIS;

EID: 70349920904     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200806338     Document Type: Article
Times cited : (54)

References (35)
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    • T. Eguchi, K. Kondo, K. Kakinuma, H. Uekusa, Y. Ohashi, K. Mizoue, Y. Qiao, J. Org. Chem. 1999, 64, 5371 - 5376. The absolute and relative stereochemistries of 1 were determined by X-ray analysis.
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    • and references therein
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    • Prepared from (R)-(-)-epichlorohydrin by a two-step sequence [1)EtMgBr, Cul, THF; 2) NaOH (55% over 2 steps)]
    • Prepared from (R)-(-)-epichlorohydrin by a two-step sequence [1)EtMgBr, Cul, THF; 2) NaOH (55% over 2 steps)]
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    • The product ratio (16/19) was assessed by 1H NMR analaysis (CDCl3, 300 MHz).
    • The product ratio (16/19) was assessed by 1H NMR analaysis (CDCl3, 300 MHz).
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    • We also attempted the cyclization before removal of the benzyl group. However, the reaction produced only many unidentified by-products
    • We also attempted the cyclization before removal of the benzyl group. However, the reaction produced only many unidentified by-products.
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    • The same reaction with (R)-valinol gave two diastereomers in high selectivity (18:1). After separation, the major isomer of the (R)-valinol adducts was converted by the same synthetic sequence described in the text. The final product was the 6,7- bis(epimer) of 2, implying that the stereochemical course of the lactone cleavage is mainly decided by the reagent control (by the chirality of the nucleophile), but not by the substrate control (by the chirality in lactone 21). For a related paper, see S. Masamune, S. A. Ali, D. L. Snitman, D. S. Garvey, Angew. Chem. 1980, 92, 573 -575;
    • The same reaction with (R)-valinol gave two diastereomers in high selectivity (18:1). After separation, the major isomer of the (R)-valinol adducts was converted by the same synthetic sequence described in the text. The final product was the 6,7- bis(epimer) of 2, implying that the stereochemical course of the lactone cleavage is mainly decided by the reagent control (by the chirality of the nucleophile), but not by the substrate control (by the chirality in lactone 21). For a related paper, see S. Masamune, S. A. Ali, D. L. Snitman, D. S. Garvey, Angew. Chem. 1980, 92, 573 -575;
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    • For preparation of SmI2 in THF, see: P. Girard, J. L. Namy, H. B. Kagan, J. Am. Soc. Chem. 1980, 102, 2693 -2698.
    • For preparation of SmI2 in THF, see: P. Girard, J. L. Namy, H. B. Kagan, J. Am. Soc. Chem. 1980, 102, 2693 -2698.
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    • 2-mediated pinacol coupling of benzaldehyde. See, H. C. Aspinall, N. Greeves, C. Valla, Org. Lett. 2005, 7, 1919-1922.
    • 2-mediated pinacol coupling of benzaldehyde. See, H. C. Aspinall, N. Greeves, C. Valla, Org. Lett. 2005, 7, 1919-1922.
  • 35
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    • D, and m.p.) of the synthetic material were to be consistent with an authentic sample of the natural product (see, Ref. [1b]), kindly provided by Prof. Dr. Tadashi Eguchi, Tokyo Institute of Technology.
    • D, and m.p.) of the synthetic material were to be consistent with an authentic sample of the natural product (see, Ref. [1b]), kindly provided by Prof. Dr. Tadashi Eguchi, Tokyo Institute of Technology.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.