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23
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20544450473
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note
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Interestingly, treatment of 7 with 5 equiv of NIS, followed by 1 equiv of water (2 h when TLC indicated no 7) gave 9 in improved 87% yield (entry 21).
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-
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25
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20544478329
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note
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Low nucleophilicity acceptors gave 47-49% glycosylsuccinimide.
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26
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20544478558
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note
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Lower yield of 31 may be from volatility.
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27
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20544453986
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note
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Three equivalents of NIS gave 60% 24 with 20% monodebenzylated- monobenzoylated 18. O-Benzyldecyl ether did not debenzylate with 3 equiv of NIS, and control of NIS (2 equiv) gave more 24 from 23.
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28
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20544472269
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note
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Products detected by TLC not necessarily present in the reaction mixture and may be the result of hydrolysis of intermediates.
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29
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20544446563
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Landoh-Bornstein, A.: Fischer, H., Hellwege, I.-H.,Springer-Verlag: Berlin, 1985; Vol. 9, Part d
-
Interestingly, reaction of 7 with 3 equiv of NIS for 3 h gave a weak, transient EPR signal showing a nitrogen 1:1:1 triplet signal (g = 2.0053, a(N) = 1.55 mT at 9.414 GHz) consistent with a nitrogen centered radical/ radical cation (a) [Landoh-Bornstein, A.: Fischer, H., Hellwege, I.-H., Eds.; Springer-Verlag: Berlin, 1985; Vol. 9, Part d.
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31
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0000804936
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(c) Shaffer, S. A.; Martin Sadílek, M.; Tureček, F. J. Org. Chem. 1996, 61, 5234] and might suggest alternative pathways. However, identical reaction outcomes were found in the absence of light, and attempts to trap putative radical intermediates, e.g., 2.5 equiv of methyl methacrylate, failed. Further mechanistic details are currently under investigation.
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Shaffer, S.A.1
Martin Sadílek, M.2
Tureček, F.3
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