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16844371856
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Valentine, J. C.; McDonald, F. E.; Neiwert, W. A.; Hardcastle, K. I. J. Am. Chem. Soc. 2005, 127, 4586 and references therein.
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33745700292
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Due to the availability of 1,2:4,5-di-O-isopropylidene-D-erythro-2,3-hexodiuro-2,6-pyranose Shi catalyst from D-fructose, we elected to prepare the enantiomers of natural products 2-4. However, an improved preparation for L-fructose is now available for the enantiomeric catalyst. See: Zhao, M.-X.; Shi, Y. J. Org. Chem. 2006, 71, 5377.
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(c) Due to the availability of 1,2:4,5-di-O-isopropylidene-D-erythro-2,3-hexodiuro-2,6-pyranose "Shi catalyst" from D-fructose, we elected to prepare the enantiomers of natural products 2-4. However, an improved preparation for L-fructose is now available for the enantiomeric catalyst. See: Zhao, M.-X.; Shi, Y. J. Org. Chem. 2006, 71, 5377.
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9
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33846843469
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For enolsilanes as terminating nucleophiles in polyene cyclizations, see: a
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For enolsilanes as terminating nucleophiles in polyene cyclizations, see: (a) Corey, E. J.; Sodeoka, M. Tetrahedron Lett. 1991, 32, 1005.
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0037174453
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13
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33846843470
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2AICl or TBSOTf favored formation of the silyl ether 10.
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2AICl or TBSOTf favored formation of the silyl ether 10.
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14
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33846789133
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See Supporting Information for details on the crystallographic analyses
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See Supporting Information for details on the crystallographic analyses.
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15
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33846823517
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We observed substantial differences in optical rotations for synthetic ent-2, ent-3, and ent-4 when compared with reported values for the corresponding natural products 2, 3, and 4. However, spectroscopic data for our synthetic compounds are in good agreement with the natural products (see Supporting Information).
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We observed substantial differences in optical rotations for synthetic ent-2, ent-3, and ent-4 when compared with reported values for the corresponding natural products 2, 3, and 4. However, spectroscopic data for our synthetic compounds are in good agreement with the natural products (see Supporting Information).
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16
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0033548555
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For analogous ring-expansion methods, see: a
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0000732375
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For examples of mechanistically similar ring contractions, see: (c) Hayashi, N, Fujiwara, K, Murai, A. Synlett 1997, 793
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For examples of mechanistically similar ring contractions, see: (c) Hayashi, N.; Fujiwara, K.; Murai, A. Synlett 1997, 793.
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21
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33846844062
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3P (1.2 equiv), NBS (1.1 equiv), THF, 0°C.
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3P (1.2 equiv), NBS (1.1 equiv), THF, 0°C.
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22
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1542755438
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33846792452
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Diene 24 was also obtained from initial conversion of enol triflate 23 to the vinylboronate, followed by cross-coupling with enol triflate 22, but the yields of 24 were substantially lower (38-42%) from this route.
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Diene 24 was also obtained from initial conversion of enol triflate 23 to the vinylboronate, followed by cross-coupling with enol triflate 22, but the yields of 24 were substantially lower (38-42%) from this route.
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