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4344710993
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note
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The difference in the rates of acylation of the hydroxyl groups on C-5(5′) and C-8(8′) in 1 is likely due to the ability of the latter to form a hydrogen bond to the carbonyl on C-1(1′). Inspeetion of molecular models suggests these two functional groups are quite close.
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26
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4344692808
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note
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It should be noted that 3 is assigned a C-8(8′) = R configuration, while 1 and 2 possess C-8(8′) configurations despite the fact that the hydroxyl groups are alpha in all three metabolites. The replacement of one of the hydrogens at C-8(8′) in 1 and 2 with a methoxyl functionality in 3 reverses the Cahn-Ingold-Prelog priorities. The same phenomenon is seen with rostratin D (4).
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27
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4344653170
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note
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The regioselective acylation of 4 is most likely due to the greater nucleophilicity of the alcohol as compared to the thiol.
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28
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0034934799
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and references therein
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Other structurally related compounds include the following. (a) Epicorazines A-C: Kleinwachter, P.; Dahse, H.-M.; Luhmann, U.; Schlegel, B.; Dornberger, K. J. Antibiot. 2001, 54, 521-525, and references therein.
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Kleinwachter, P.1
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Luhmann, U.3
Schlegel, B.4
Dornberger, K.5
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29
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0010410676
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(b) Epoxyexserohilone: Cutler, H. G.; Hoogsteen, K.; Littrell, R. H.; Arison, B. H. Agric. Biol. Chem. 1991, 55, 2037-2042. We thank the reviewer who brought the latter example to our attention.
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Hoogsteen, K.2
Littrell, R.H.3
Arison, B.H.4
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