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The much faster rate of hydroboration using this method as compared to thexylchloroborane was thought to be advantageous since the protected homoallylic alcohol would remain in contact with the chloroborane for a much shorter time and at a lower temperature, which should minimize side reactions.
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57
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85034180120
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Since an excess of MegSiH was not found to have any deleterious effect on the reaction, a moderate excess (1.5 equiv) of it was used to avoid having to measure accurately this low-boiling (bp 7 °C) liquid.
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58
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85034189039
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note
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To find the amount of scrambling, the trialkylborane 15 in each case was converted into the unsymmetrical ketone 17, as described in this paper. The amounts of di-ra-hexyl ketone and di-n-octyl ketone formed along with this unsymmetrical ketone 17 gave a direct measure of the amount of scrambling.
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13C NMR since any racemization would have resulted in the formation of diastereomers of 28. Further, the enantiomeric purity of the spiroketal 29 was confirmed by chiral capillary GC in comparison with the racemic spiroketal.
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