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9
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10
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0942265463
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11
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13644265523
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a) J. H. Ju, S. K. Lim, H. Jiang, B. Shen, J. Am. Chem. Soc. 2005, 127, 1622-1623;
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Ju, J.H.1
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Jiang, H.3
Shen, B.4
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12
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24144485444
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b) J. H. Ju, S. K. Lim, H. Jiang, J. W. Seo, B. Shen, J. Am. Chem. Soc. 2005, 127, 11930-11931;
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Ju, J.H.1
Lim, S.K.2
Jiang, H.3
Seo, J.W.4
Shen, B.5
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13
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33846288885
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c) J. H. Ju, S. K. Lim, H. Jiang, J. W. Seo, Y. Her, B. Shen, Org. Lett. 2006, 8, 5865-5868.
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Ju, J.H.1
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Her, Y.5
Shen, B.6
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17
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34547174356
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A trace quantity of the α-oxiranyl β-anomeric lactol was also observed see Supporting Information
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A trace quantity of the α-oxiranyl β-anomeric lactol was also observed (see Supporting Information).
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19
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85022622903
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Y. Egawa, T. Okuda, M. Suzuki, Chem. Pharm. Bull. 1963, 11, 589.
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(1963)
Chem. Pharm. Bull
, vol.11
, pp. 589
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Egawa, Y.1
Okuda, T.2
Suzuki, M.3
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20
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4043165745
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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.
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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.
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21
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0000130755
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a) J. A. Marshall, J. D. Trometer, B. E. Blough, T. D. Crute, J. Org. Chem. 1988, 53, 4274-4282;
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J. Org. Chem
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Marshall, J.A.1
Trometer, J.D.2
Blough, B.E.3
Crute, T.D.4
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23
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0001724522
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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)
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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)
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24
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34547174858
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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 %.
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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 %.
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25
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33845282886
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a) E. J. Corey, R. K. Bakshi, S. Shibata, J. Am. Chem. Soc. 1987, 109, 5551-5553;
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(1987)
J. Am. Chem. Soc
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, pp. 5551-5553
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Corey, E.J.1
Bakshi, R.K.2
Shibata, S.3
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27
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0032541271
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Angew. Chem. Int. Ed. 1998, 37, 1986-2012;
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(1998)
Chem. Int. Ed
, vol.37
, pp. 1986-2012
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Angew1
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28
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33845282438
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c) E. J. Corey, C. K. Bakshi, S. Shibata, C. P. Chen, V. K. Singh, J. Am. Chem. Soc. 1987,109, 7925-7926.
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(1987)
J. Am. Chem. Soc
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Corey, E.J.1
Bakshi, C.K.2
Shibata, S.3
Chen, C.P.4
Singh, V.K.5
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29
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34547196473
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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.
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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.
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30
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34547200626
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See the Supporting Information for preparation of 24
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See the Supporting Information for preparation of 24.
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31
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0037134804
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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.
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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.
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32
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34547204687
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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.
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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.
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33
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34547160947
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Natural material was graciously provided by B. Shen and coworkers
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Natural material was graciously provided by B. Shen and coworkers.
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34
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33751156723
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Previous examples of phosphine-catalyzed E-Z equilibration: a C. Zhang, X. Lu, J. Org. Chem. 1995, 60, 2906-2908;
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Previous examples of phosphine-catalyzed E-Z equilibration: a) C. Zhang, X. Lu, J. Org. Chem. 1995, 60, 2906-2908;
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36
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34547206271
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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
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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).
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37
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0001588766
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For a discussion of the Curtin-Hammet principle, which is relevant to this discussion, see
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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.
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(1987)
Pure Appl. Chem
, vol.59
, pp. 1661-1672
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Seeman, J.I.1
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