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24
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0041405219
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note
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It was straightforward to prepare the corresponding benzyl ether by using the Evans oxazolidinone alkylation procedure with chloromethylbenzyl ether as the alkylating agent, and the derived β-benzyloxy methyl ketone intermediate was used sucessfully in condensation with aldehyde 6. However, all attempts to remove the benzyl ether at the stage of intermediate 21 were either compromised by olefin reduction or by acetate migration. Also, it proved impractical to prepare the p-methoxybenzyl ether 18 using the simple sequence employed to prepare the corresponding benzyl ether.
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25
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0041405214
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Gleason, J.L.6
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15844376790
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Yang, M.G.4
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28
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0041906334
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note
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β and the aldehyde oxygen, while interchanging H and the O substituent will give both a diaxial steric interaction and also maximum dipole-dipole repulsion between the two C-O bonds. Although there might be some ambiguity about which of these alternative arrangements would be favored, it is a certainty that both would be considerably higher in energy than the preferred arrangement depicted.
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29
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0033515504
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Keck, G. E.; Wager, C. A.; Sell, T.; Wager, T. T. J. Org. Chem. 1999, 64, 2172.
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Keck, G.E.1
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Sell, T.3
Wager, T.T.4
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30
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0041405218
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note
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A similar level of stereoselectivity was obtained using tetramethylammonium triacetoxyborohydride reduction. In contrast, both reductions were completely stereoselective for the anti diol when conducted on the corresponding benzyl compound (19 with PMB replaced by benzyl).
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31
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0042407570
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note
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The spectral and analytical data for 1 were in excellent agreement with that previously reported for the natural material and that from previous synthetic efforts.
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