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17
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77955141706
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Obtained from meso -diol (2 R*,3 S*,4 S*)-3-(tert -butyldimethylsilyloxy)-2,4-dimethyl-1,5-pentanediol 32 according to reported procedures; see refs 6 and 7
-
Obtained from meso -diol (2 R*,3 S*,4 S*)-3-(tert -butyldimethylsilyloxy)-2,4-dimethyl-1,5-pentanediol 32 according to reported procedures; see refs 6 and 7.
-
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18
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33845282886
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Corey, E. J.; Bakshi, R. K.; Shibata, S. J. Am. Chem. Soc. 1987, 109, 5551
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33845282438
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0001513454
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For application to propargylic ketones, see
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For application to propargylic ketones, see: Parker, K. A.; Ledeboer, M. W. J. Org. Chem. 1996, 61, 3214
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Parker, K.A.1
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23
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84855638301
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-
1H NMR analysis and/or GC/MS analysis of the crude reaction mixture
-
1H NMR analysis and/or GC/MS analysis of the crude reaction mixture.
-
-
-
-
24
-
-
0343193338
-
-
For recent examples in synthesis, see
-
For recent examples in synthesis, see: Witulski, B.; Bergsträber, U.; Gössmann, M. Tetrahedron 2000, 56, 4747
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(2000)
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Witulski, B.1
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26
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61449179275
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Paterson, I.; Mühltau, F. A.; Cordier, C. J.; Housden, M. P.; Burton, P. M.; Loiseleur, O. Org. Lett. 2009, 11 (2) 353
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Paterson, I.1
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Cordier, C.J.3
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Burton, P.M.5
Loiseleur, O.6
-
27
-
-
84855620548
-
-
2 was used without any acid at 40 °C, no conversion of the alkyne was noticed, whereas at 70 °C, the silyl ethers were cleaved
-
2 was used without any acid at 40 °C, no conversion of the alkyne was noticed, whereas at 70 °C, the silyl ethers were cleaved.
-
-
-
-
28
-
-
45249087646
-
-
Prepared according to a reported procedure by;;; Wiley: New York,; Collect
-
Prepared according to a reported procedure by Johns, B. A.; Grant, C. M.; Marshall, J. M. Organic Synthesis; Wiley: New York, 2004; Collect. Vol. X, p 170.
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(2004)
Organic Synthesis
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Johns, B.A.1
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0347760049
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Wiskur, S. L.; Korte, A.; Fu, G. C. J. Am. Chem. Soc. 2004, 126, 82
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Wiskur, S.L.1
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30
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33847801219
-
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For the hydrozirconation step, see
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For the hydrozirconation step, see: Hart, D. W.; Blackburn, T. F.; Schwartz, J. J. Am. Chem. Soc. 1975, 97, 679
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Hart, D.W.1
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33
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0037074093
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Mitchell, I. S.; Pattenden, G.; Stonehouse, J. P. Tetrahedron Lett. 2002, 43, 493
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Mitchell, I.S.1
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-
34
-
-
84855638302
-
-
4F in MeOH
-
4F in MeOH.
-
-
-
-
35
-
-
0035802349
-
-
This method was successfully used by Paterson et al. in their synthesis of spirangien A. See ref 3 and
-
This method was successfully used by Paterson et al. in their synthesis of spirangien A. See ref 3 and Paterson, I.; Florence, G. J.; Gerlach, K.; Scott, J. P.; Sereinig, N. J. Am. Chem. Soc. 2001, 123, 9535
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(2001)
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Paterson, I.1
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Sereinig, N.5
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36
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0034677179
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Paterson, I.; Florence, G. J.; Gerlach, K.; Scott, J. P. Angew. Chem., Int. Ed. 2000, 39, 377
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(2000)
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Paterson, I.1
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Scott, J.P.4
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37
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0000194961
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Paterson, I.; Goodman, J. M.; Lister, M. A.; Schumann, R. C.; McClure, C. K.; Norcross, R. D. Tetrahedron Lett. 1990, 46, 4663
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(1990)
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Paterson, I.1
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McClure, C.K.5
Norcross, R.D.6
-
38
-
-
0037077057
-
-
1H NMR spectrum of the crude product. Assignment of each diastereomer was hypothesized by analysis of the ABX pattern of the C22 methylene unit; see:;;;;;;;;, See Supporting Information for details. The stereochemistry was also confirmed by NOESY studies on spiroketal 22, see Supporting Information for details
-
1H NMR spectrum of the crude product. Assignment of each diastereomer was hypothesized by analysis of the ABX pattern of the C22 methylene unit; see: Roush, W. R.; Bannister, T. D.; Wendt, M. D.; VanNieuwenhze, M. S.; Gustin, D. J.; Dilley, G. J.; Lane, G. C.; Scheidt, K. A.; Smith, W. J. J. Org. Chem. 2002, 67, 4284 See Supporting Information for details. The stereochemistry was also confirmed by NOESY studies on spiroketal 22, see Supporting Information for details.
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(2002)
J. Org. Chem.
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, pp. 4284
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Roush, W.R.1
Bannister, T.D.2
Wendt, M.D.3
Vannieuwenhze, M.S.4
Gustin, D.J.5
Dilley, G.J.6
Lane, G.C.7
Scheidt, K.A.8
Smith, W.J.9
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39
-
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70449371845
-
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For a detailed study, see
-
For a detailed study, see: Lorenz, M.; Bluhm, N.; Kalesse, M. Synthesis 2009, 3061
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(2009)
Synthesis
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Lorenz, M.1
Bluhm, N.2
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4243660022
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Arnarp, J.; Kenne, L.; Lindberg, B.; Lönngren, J. Carbohydr. Res. 1975, 44, C5-C7
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Arnarp, J.1
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41
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0023872527
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For examples, see
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For examples, see: Walba, D. M.; Thurmes, W. N.; Haltiwanger, R. C. J. Org. Chem. 1988, 53, 1046
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Haltiwanger, R.C.6
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42
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0029166622
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Paterson, I.; Ward, R. A.; Smith, J. D.; Cumming, J. G.; Yeung, K.-S. Tetrahedron 1995, 51, 9437
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(1995)
Tetrahedron
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Paterson, I.1
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Yeung, K.-S.5
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43
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12944276969
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ONeill, J. A.; Gallagher, O. P.; Devine, K. J.; Jones, P. W.; Maguire, A. R. J. Nat. Prod. 2005, 68, 125
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Oneill, J.A.1
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Maguire, A.R.5
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44
-
-
84855632543
-
-
2] an excess of the reagents at 50 °C was required in order to reach full conversion of 19, but a partial degradation was also observed thus explaining the moderate 50% yield
-
2] an excess of the reagents at 50 °C was required in order to reach full conversion of 19, but a partial degradation was also observed thus explaining the moderate 50% yield.
-
-
-
-
45
-
-
77955151534
-
-
Hypothetical structure for 33
-
Hypothetical structure for 33
-
-
-
-
46
-
-
77955148715
-
-
This side reaction was not observed by Paterson et al. (3, 4) probably because acetonide protecting groups are more labile than TBS ethers, thus allowing the use of soft acidic conditions for their deprotection. Kalesse et al. (4) clearly mentioned that when TBS ethers were used instead of TES ethers the deprotection/spiroketalisation step failed
-
This side reaction was not observed by Paterson et al. (3, 4) probably because acetonide protecting groups are more labile than TBS ethers, thus allowing the use of soft acidic conditions for their deprotection. Kalesse et al. (4) clearly mentioned that when TBS ethers were used instead of TES ethers the deprotection/spiroketalisation step failed.
-
-
-
-
47
-
-
84855632541
-
-
The protection of the C27 hydroxyl group as a PMB ether was first envisioned in order to avoid the side reaction observed during the HF·Py mediated spiroketalization step. Unfortunately, the iron-catalyzed cross-coupling of 34 with (E)-1-methyl-1-propenylmagnesium bromide failed in the presence of the PMB ether group, and consequently, the synthesis of the aldehyde partner for the aldol coupling could not be completed
-
The protection of the C27 hydroxyl group as a PMB ether was first envisioned in order to avoid the side reaction observed during the HF·Py mediated spiroketalization step. Unfortunately, the iron-catalyzed cross-coupling of 34 with (E)-1-methyl-1-propenylmagnesium bromide failed in the presence of the PMB ether group, and consequently, the synthesis of the aldehyde partner for the aldol coupling could not be completed.
-
-
-
-
48
-
-
0000246027
-
-
Hans Meerwein, H.; Hinz, G.; Hofmann, P.; Kroning, E.; Pfeil, E. J. Prakt. Chem. 1937, 147, 257
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Hans Meerwein, H.1
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Pfeil, E.5
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49
-
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0028021609
-
-
Also see refs 3 and 4
-
Evans, D. A.; Ratz, A. M.; Huff, B. E.; Sheppard, G. S. Tetrahedron Lett. 1994, 35, 7171 Also see refs 3 and 4.
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Evans, D.A.1
Ratz, A.M.2
Huff, B.E.3
Sheppard, G.S.4
-
50
-
-
77955156786
-
-
At this stage, we had to transform the carbamate group into an iodide in order to install the C30-C31 double bond by mean of an iron-catalyzed cross-coupling. In that goal, we first envisioned a protection of the four alcohols as TES ethers, but unfortunately, a degradation of the substrate was observed in presence of TESOTf, thus unabling us to complete the synthesis of spiroketal 1
-
At this stage, we had to transform the carbamate group into an iodide in order to install the C30-C31 double bond by mean of an iron-catalyzed cross-coupling. In that goal, we first envisioned a protection of the four alcohols as TES ethers, but unfortunately, a degradation of the substrate was observed in presence of TESOTf, thus unabling us to complete the synthesis of spiroketal 1.
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-
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