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28044468455
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note
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Migual Carda and Alberto Marco noted that various stereoisomers of spicigerolide (2) have improved cytotoxicity against several cancer cell lines; see ref 5b.
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(a) Ahmed, Md. M.; Berry, B. P.; Hunter, T. J.; Tomcik, D. J.; O'Doherty, G. A. Org. Lett. 2005, 7, 745-748.
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For other uses of this pyranone formation in synthesis, see ref 3 and: (c) Pradaux, F.; Bouzbouz, S. Org. Lett. 2001, 3, 2233-2235.
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0343072430
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We initially considered the use of the catalytic asymmetric allylation reagent developed by Keck but were dissuaded by its use of stoichiometric tin. See: (a) Keck, G. E.; Krishnamurthy, D. Org. Synth. 1997, 75, 12.
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12344315246
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In contrast to our results for acetonide 14 and its corresponding diol, Smith observed excellent regiocontrol (>10:1) in the dihydroxylation of related substituted epoxytrienoates. Similarly, they observed no significant loss of stereocontrol in the mismatched (slower) case. See: Smith, A. B., III; Walsh, S. P.; Frohn, M.; Duffey, M. O. Org. Lett. 2005, 7, 139-142.
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28044459717
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note
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2PHAL, see Scheme 3).
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32
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28044452042
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note
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The lack of E/Z selectivity (1:1) in the Wittig reaction with aldehyde 21 is quite surprising when compared to the nearly identical Wittig reaction with the C-5 diastereomeric aldehyde 13, where the E isomer 6b was formed with almost 10:1 selectivity. Although we cannot offer an explanation for this result, we did find this result to be reproducible.
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28044459028
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note
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2 reagent for this transformation; see ref 5a-d. We have found that the Leighton reagent works equally well in terms of stereochemical outcome and allows for a significantly simpler product isolation procedure; see ref 9.
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34
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33947086629
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1H NMR of the corresponding Mosher esters. See: Sullivan, G. R.; Dale, J. A.; Mosher, H. S. J. Org. Chem. 1973, 38, 2143.
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Sullivan, G.R.1
Dale, J.A.2
Mosher, H.S.3
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28044473257
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note
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Experimental procedures for the synthesis of anamarine are presented in the Experimental Section. Complete experimental procedures and spectral data for all compounds are presented in the Supporting Information.
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36
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28044453141
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note
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These structures are not shown in the text.
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