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Volumn 46, Issue 29, 2007, Pages 5576-5579

Total synthesis of (+)-isomigrastatin

Author keywords

Inhibitors; Isomerization; Metathesis; Natural products; Total synthesis

Indexed keywords

METATHESIS; NATURAL PRODUCTS; TOTAL SYNTHESIS;

EID: 34547183333     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200701837     Document Type: Article
Times cited : (35)

References (37)
  • 17
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    • A trace quantity of the α-oxiranyl β-anomeric lactol was also observed see Supporting Information
    • A trace quantity of the α-oxiranyl β-anomeric lactol was also observed (see Supporting Information).
  • 20
    • 4043165745 scopus 로고    scopus 로고
    • There is precedent for Wittig and Horner-Emmons couplings directly with 2,3-epoxylactols: see J. E. Harvey, S. A. Raw, R. J. K. Taylor, Org. Lett. 2004, 6, 2611-2614. The difficulty in our case may have been due to the presence of an additional methyl group adjacent to the anomeric carbon center.
    • There is precedent for Wittig and Horner-Emmons couplings directly with 2,3-epoxylactols: see J. E. Harvey, S. A. Raw, R. J. K. Taylor, Org. Lett. 2004, 6, 2611-2614. The difficulty in our case may have been due to the presence of an additional methyl group adjacent to the anomeric carbon center.
  • 23
    • 0001724522 scopus 로고    scopus 로고
    • N2′ result, possibly owing to the larger size of the glutarimide appendage (R′, Scheme 3) relative to the methyl group in Marshall's system. (Chemical Equation Presented)
    • N2′ result, possibly owing to the larger size of the glutarimide appendage (R′, Scheme 3) relative to the methyl group in Marshall's system. (Chemical Equation Presented)
  • 24
    • 34547174858 scopus 로고    scopus 로고
    • N2′ reaction as a mixture with 19, from which it was virtually inseparable. However, the corresponding products 21 and 22 were easily separated and isolated with a combined yield of 75 %.
    • N2′ reaction as a mixture with 19, from which it was virtually inseparable. However, the corresponding products 21 and 22 were easily separated and isolated with a combined yield of 75 %.
  • 27
    • 0032541271 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 1998, 37, 1986-2012;
    • (1998) Chem. Int. Ed , vol.37 , pp. 1986-2012
    • Angew1
  • 29
    • 34547196473 scopus 로고    scopus 로고
    • Numerous ring-closing metathesis strategies failed to give the required (2,3),(6,7)-dienolide directly, whether closure was attempted at the 2,3- or 6,7-positions. This was likely due to decomposition of this unstable motif under metathesis conditions.
    • Numerous ring-closing metathesis strategies failed to give the required (2,3),(6,7)-dienolide directly, whether closure was attempted at the 2,3- or 6,7-positions. This was likely due to decomposition of this unstable motif under metathesis conditions.
  • 30
    • 34547200626 scopus 로고    scopus 로고
    • See the Supporting Information for preparation of 24
    • See the Supporting Information for preparation of 24.
  • 31
    • 0037134804 scopus 로고    scopus 로고
    • 1HNMR signals showed a 1.6:1 ratio favoring the Z geometry at C6-C7 for each C2 epimer. Future efforts will be directed toward enhancement of yield and selectivity. For a promising direction, see: A. Fürstner, K. Radkowski, C Wirtz, R. Goddard, C. W. Lehmann, R. Mynott, J. Am. Chem. Soc. 2002, 124, 7061-7069.
    • 1HNMR signals showed a 1.6:1 ratio favoring the Z geometry at C6-C7 for each C2 epimer. Future efforts will be directed toward enhancement of yield and selectivity. For a promising direction, see: A. Fürstner, K. Radkowski, C Wirtz, R. Goddard, C. W. Lehmann, R. Mynott, J. Am. Chem. Soc. 2002, 124, 7061-7069.
  • 32
    • 34547204687 scopus 로고    scopus 로고
    • The major C2 epimer eliminated along C2-C3 to give a separable 9:1 mixture of E and Z products. The minor C2 epimer afforded exclusively the E isomer.
    • The major C2 epimer eliminated along C2-C3 to give a separable 9:1 mixture of E and Z products. The minor C2 epimer afforded exclusively the E isomer.
  • 33
    • 34547160947 scopus 로고    scopus 로고
    • Natural material was graciously provided by B. Shen and coworkers
    • Natural material was graciously provided by B. Shen and coworkers.
  • 34
    • 33751156723 scopus 로고    scopus 로고
    • Previous examples of phosphine-catalyzed E-Z equilibration: a C. Zhang, X. Lu, J. Org. Chem. 1995, 60, 2906-2908;
    • Previous examples of phosphine-catalyzed E-Z equilibration: a) C. Zhang, X. Lu, J. Org. Chem. 1995, 60, 2906-2908;
  • 36
    • 34547206271 scopus 로고    scopus 로고
    • This isomerization could also be effected by excessive exposure to silica gel or weak nucleophiles such as pyridine. The silicapromoted rearrangement also afforded a substantial quantity of migrastatin 2
    • This isomerization could also be effected by excessive exposure to silica gel or weak nucleophiles such as pyridine. The silicapromoted rearrangement also afforded a substantial quantity of migrastatin (2).
  • 37
    • 0001588766 scopus 로고
    • For a discussion of the Curtin-Hammet principle, which is relevant to this discussion, see
    • For a discussion of the Curtin-Hammet principle, which is relevant to this discussion, see: J. I. Seeman, Pure Appl. Chem. 1987, 59, 1661-1672.
    • (1987) Pure Appl. Chem , vol.59 , pp. 1661-1672
    • Seeman, J.I.1


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.