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J. Malmstrom, C. Christophersen, A.F. Barrero, J.E. Oltra, J. Justicia, and A. Rosales J. Nat. Prod. 65 2002 364 367
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Malmstrom, J.1
Christophersen, C.2
Barrero, A.F.3
Oltra, J.E.4
Justicia, J.5
Rosales, A.6
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2
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64549096370
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For a comparison of this new catalytic method to other dihydrofuran strategies, consult: M. Brichacek, and J.T. Njardarson Org. Biomol. Chem. 7 2009 1761 1770
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(2009)
Org. Biomol. Chem.
, vol.7
, pp. 1761-1770
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Brichacek, M.1
Njardarson, J.T.2
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4
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70350303174
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N.A. McGrath, E.S. Bartlett, S. Sittihan, and J.T. Njardarson Angew. Chem., Int. Ed. 48 2009 8543 8546
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(2009)
Angew. Chem., Int. Ed.
, vol.48
, pp. 8543-8546
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McGrath, N.A.1
Bartlett, E.S.2
Sittihan, S.3
Njardarson, J.T.4
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6
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77954244226
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Total synthesis of natural (+)-varitriol (1):
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Total synthesis of natural (+)-varitriol (1):
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8
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60849121714
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M. Palik, O. Karlubikova, A. Lasikova, J. Kozisek, and T. Gracza Eur. J. Org. Chem. 2009 709 715
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Eur. J. Org. Chem.
, pp. 709-715
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Palik, M.1
Karlubikova, O.2
Lasikova, A.3
Kozisek, J.4
Gracza, T.5
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9
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77954242832
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Total synthesis of (-)-varitriol (2):
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Total synthesis of (-)-varitriol (2):
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12
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77954244431
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Two studies dedicated to constructing varitriol analogs have been reported in the literature:
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Two studies dedicated to constructing varitriol analogs have been reported in the literature:
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15
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77949791510
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An additional chiral approach was published online February 24, 2010. S. Ghosh, and T.K. Pradhap J. Org. Chem. 75 2010 2107 2110
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(2010)
J. Org. Chem.
, vol.75
, pp. 2107-2110
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Ghosh, S.1
Pradhap, T.K.2
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16
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77954243473
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Although Taylor's synthesis is expedient and beautifully assembles the enantiomer of varitriol (2) it is worth noting that unnatural l-Ribose, which would be needed to access (+)-varitriol (1), is prohibitively expensive and therefore not a suitable chiral starting material.
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Although Taylor's synthesis is expedient and beautifully assembles the enantiomer of varitriol (2) it is worth noting that unnatural l-Ribose, which would be needed to access (+)-varitriol (1), is prohibitively expensive and therefore not a suitable chiral starting material.
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21
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0000443501
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M. Frohn, M. Dalkiewicz, Y. Tu, Z.-X. Wang, and Y. Shi J. Org. Chem. 63 1998 2948 2953
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(1998)
J. Org. Chem.
, vol.63
, pp. 2948-2953
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Frohn, M.1
Dalkiewicz, M.2
Tu, Y.3
Wang, Z.-X.4
Shi, Y.5
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22
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77954242305
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In concert with our goal of making the sequence as practical as possible, we have also successfully ring expanded the mixture of epoxides (5/6 and 13/14) obtained from the dienes 4 and 12 to 2,5-dihydrofurans 7 and 15, thus eliminating the need for chromatographically separating the two vinyl oxirane constitutional isomers. These ring expansions have been performed on gram scale.
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In concert with our goal of making the sequence as practical as possible, we have also successfully ring expanded the mixture of epoxides (5/6 and 13/14) obtained from the dienes 4 and 12 to 2,5-dihydrofurans 7 and 15, thus eliminating the need for chromatographically separating the two vinyl oxirane constitutional isomers. These ring expansions have been performed on gram scale.
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24
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77954242197
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For similar Darzen reaction examples employing a bromo acrylate and acrolein derivatives to access vinyl oxiranes like 20, see:
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For similar Darzen reaction examples employing a bromo acrylate and acrolein derivatives to access vinyl oxiranes like 20, see:
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27
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77954243801
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By using an acyl pyrrole variant of 17 instead of a t-butyl ester an asymmetric variant of 20 could be accessed following Shibasaki's impressive epoxidation protocol.
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By using an acyl pyrrole variant of 17 instead of a t-butyl ester an asymmetric variant of 20 could be accessed following Shibasaki's impressive epoxidation protocol.
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28
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0142087735
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T. Kinoshita, S. Okada, S.-R. Park, S. Matsunaga, and M. Shibasaki Angew. Chem., Int. Ed. 42 2003 4680 4684
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(2003)
Angew. Chem., Int. Ed.
, vol.42
, pp. 4680-4684
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Kinoshita, T.1
Okada, S.2
Park, S.-R.3
Matsunaga, S.4
Shibasaki, M.5
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29
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2942635094
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S. Matsunaga, T. Kinashita, S. Okada, S. Harada, and M. Shibasaki J. Am. Chem. Soc. 126 2004 7559 7570
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(2004)
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, vol.126
, pp. 7559-7570
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Matsunaga, S.1
Kinashita, T.2
Okada, S.3
Harada, S.4
Shibasaki, M.5
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30
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58149151106
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Interestingly, the equivalent aziridine substrate of 19 does successfully ring expand M. Brichacek, D. Lee, and J.T. Njardarson Org. Lett. 10 2008 5023 5026 We attribute this difference to the fact that the aziridine nitrogen atom coordinates more effectively to the copper catalyst than the oxirane oxygen atom and the competing hydride shift pathway the vinyl oxirane substrates need to overcome, while the aziridines do not
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(2008)
Org. Lett.
, vol.10
, pp. 5023-5026
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Brichacek, M.1
Lee, D.2
Njardarson, J.T.3
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31
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77954244575
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3
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3
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32
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77954243998
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This product could be used to access varitriol analogs.
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This product could be used to access varitriol analogs.
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34
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0347090287
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We have been able to find only one example in the literature, wherein an acrylate group is exchanged for a terminal olefin. This was accomplished in modest yields using Grubbs second generation catalyst and ethylene: M.G. Banwell, and D.T.J. Loong Heterocycles 62 2004 713 734
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(2004)
Heterocycles
, vol.62
, pp. 713-734
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Banwell, M.G.1
Loong, D.T.J.2
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35
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4143062538
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T.R. Hoye, C.S. Jeffrey, M.A. Tennakoon, J. Wang, and H. Zhao J. Am. Chem. Soc. 126 2004 10210 10211
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Hoye, T.R.1
Jeffrey, C.S.2
Tennakoon, M.A.3
Wang, J.4
Zhao, H.5
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36
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1842863015
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N. Halland, A. Braunton, S. Bachmann, M. Marigo, and K.A. Jorgensen J. Am. Chem. Soc. 126 2004 4790 4791
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Halland, N.1
Braunton, A.2
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Marigo, M.4
Jorgensen, K.A.5
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38
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0037463034
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We also considered epoxidizing the known (E,E)-diene homoallylic alcohol using Yamamoto's new asymmetric epoxidation protocol: N. Makita, Y. Hoshino, and H. Yamamoto Angew. Chem., Int. Ed. 42 2003 941 943
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(2003)
Angew. Chem., Int. Ed.
, vol.42
, pp. 941-943
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Makita, N.1
Hoshino, Y.2
Yamamoto, H.3
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