Total synthesis and stereochemistry of pinnatoxins B and C

Organic Letters

Volumn 8, Issue 15, 2006, Pages 3327-3330

  Matsuura, Fumiyoshi ^a   Hao, Junliang ^a   Reents, Reinhard ^a   Kishi, Yoshito ^a  

^a HARVARD UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOL DERIVATIVE; PINNATOXIN B; PINNATOXIN C; SPIRO COMPOUND;

ARTICLE; CHEMICAL STRUCTURE; CHEMISTRY; NUCLEAR MAGNETIC RESONANCE; SHELLFISH; STEREOISOMERISM; SYNTHESIS;

ALCOHOLS; MOLECULAR STRUCTURE; NUCLEAR MAGNETIC RESONANCE, BIOMOLECULAR; SHELLFISH; SPIRO COMPOUNDS; STEREOISOMERISM;

EID: 33746889747     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol0611548     Document Type: Article

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27. Although C32-H and C34-H initially appeared to be useful diagnostic signals for comparison purposes, we found that their chemical shifts vary significantly depending on the sample preparation and concentration. Thus, unless these spectra were recorded under identical conditions, they cannot be used to differentiate PnTXs B and C. However, we did observe that the relative chemical shifts of C32-H for PnTXs B and C remain unchanged under various conditions. For details, see the Supporting Information.
28. 1H NMR spectrum of the synthetic PnTX C (contaminated with 5-10% of PnTX B) doped with a small amount of natural PnTX B/C (ca. 1:1 mixture) and observed no signals doubled, except that the intensity of C32-H, C29-H, C28-H, and C37-H peaks, corresponding to the contaminated PnTX B, increased noticeably. For details, see the Supporting Information.
29. 1H NMR spectra between the synthetic and natural samples, we found that the chemical shifts for the C37 methyl groups were different from the originally reported figures and should be δ = 1.04 ppm for PnTX B and δ = 1.05 ppm for PnTX C. For details, see the Supporting Information.
30. Preliminary mice acute toxicity assays showed that both synthetic PnTXs B and C exhibit comparable activity at the dose of 0.1 mg/kg. We thank Professor D. Uemura and Dr. M. Kita at Nagoya University, Nagoya, Japan, for the assays.