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0141441539
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note
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In the present context, the 6-O-trityl group of the previous epoxide 1 was replaced with the benzyl group because of the greater stability of the latter to a wide range of reaction conditions.
-
-
-
-
30
-
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0141664552
-
-
note
-
1H NMR spectrum a few minutes after the addition of the base.
-
-
-
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31
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0032564933
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Danishefsky, S.J.8
-
32
-
-
0141553072
-
-
note
-
Less than 5% of the corresponding anti 1,2-addition products were present in some cases. Products from an α-1,4 addition process were not observed at all.
-
-
-
-
33
-
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0141664551
-
-
note
-
Under protocol B, it was hoped that the organometallic reagents might behave as a base and thereby promote epoxide formation from hydroxy mesylate 3 and then undergo an addition reaction.
-
-
-
-
34
-
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0141664553
-
-
note
-
This observation indicates that alkyllithium and PhLi do not behave, in the present case, as a base, which is necessary for the cyclization of hydroxy mesylate 3 to epoxide 4.
-
-
-
-
35
-
-
0141664554
-
-
note
-
The only exception is given by the β-methyl derivative 10β [δ C(5) = 73.79 ppm]. However, the β-C-glycosidic configuration for this compound was firmly established by corresponding NOE experiment.
-
-
-
-
36
-
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0035105609
-
-
and pertinent references therein
-
Bertozzi, F.; Crotti, P.; Feringa, B. L.; Macchia, F.; Pineschi, M. Synthesis 2001, 483 and pertinent references therein.
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Bertozzi, F.1
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Macchia, F.4
Pineschi, M.5
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37
-
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0141664555
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note
-
From t-BuOK used for the cyclization of 3 to epoxide 4.
-
-
-
-
38
-
-
0141776420
-
-
note
-
As suggested by a Rewiever, epoxide 4 is not a necessary intermediate for the generation of 16 and 17, via protocol B. A Grob fragmentation process on hydroxy mesylate 3 could lead directly to the observed products.
-
-
-
-
39
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0001312924
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Trost, B. M., Fleming, I., Pattenden, G., Eds.; Pergamon: Oxford
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Rickborn, B. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Pattenden, G., Eds.; Pergamon: Oxford, 1991; Vol 3, pp 733-775.
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