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We envisioned that by incorporating a late-stage ketone reduction the new route would be amenable to the incorporation of a tritium label. For similar examples of label incorporation, see: Weigel, T. M.; Liu, H.-W. Tetrahedron Lett. 1988, 29, 4221-4224.
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0347022328
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An Achmatowicz reaction is the oxidative rearrangement of furfuryl alcohols to 2-substituted 6-hydroxy-2H-pyran-3(6H)-ones; see: (a) Achmatowicz, O.; Bielski, R. Carbohydr. Res. 1977, 55, 165-176.
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26
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24944573081
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note
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2).
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27
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0037461125
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For other examples of a catalytic TEMPO oxidation to form carboxylic acids in unprotected carbohydrates see: a) Ying, L.; Gervay-Hague, J. Carbohydrate Res. 2003, 338, 835-841.
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Ying, L.1
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0036721758
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(b) Bragd, P. L.; Besemer, A. C.; Bekkum, H. V. Carbohydr. Polym. 2002, 49, 397-406.
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Bragd, P.L.1
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Bekkum, H.V.3
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29
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24944438300
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note
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D of -82 (c 0.1). Both values were measured in methanol.
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30
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24944460292
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note
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These overall yields for 1, 19, and 21 are very similar from pentynol 9 (24, 31, and 25%, respectively).
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