Unusual transannular cyclization products of sarcophytoxide, a 14-membered marine cembranoid: Anomalous stereochemistry of epoxide-ketone rearrangement

Organic Letters

Volumn 8, Issue 14, 2006, Pages 2957-2960

  Nii, Keiji ^a   Tagami, Keiko ^a   Matsuoka, Keisuke ^a   Munakata, Tatsuo ^b   Ooi, Takashi ^a   Kusumi, Takenori ^a  

^a UNIVERSITY OF TOKUSHIMA   (Japan)

^b TOHWA UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

DITERPENE; DRUG DERIVATIVE; EPOXIDE; GAMMA BUTYROLACTONE; KETONE; SARCOPHINE; SARCOPHYTOXIDE;

ANIMAL; ANTHOZOA; ARTICLE; CHEMICAL STRUCTURE; CHEMISTRY; CONFORMATION; CYCLIZATION; HUMAN; MARINE BIOLOGY; STEREOISOMERISM; SYNTHESIS; X RAY CRYSTALLOGRAPHY;

4-BUTYROLACTONE; ANIMALS; ANTHOZOA; CRYSTALLOGRAPHY, X-RAY; CYCLIZATION; DITERPENES; EPOXY COMPOUNDS; HUMANS; KETONES; MARINE BIOLOGY; MOLECULAR CONFORMATION; MOLECULAR STRUCTURE; STEREOISOMERISM;

EID: 33746617489     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol0608404     Document Type: Article

References (15)

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9. 3), in benzene (25 mL) cooled in an icebath was added TMSOTf (0.15 mL, 0.5 equiv), and the mixture was stirred for 10 min and then stirred at room temperature for 20 min. The solution was washed with a sodium bicarbonate solution and water and then dried over sodium sulfate. Evaporation of the solvent afforded a residue (496 mg), which was subjected to silica gel chromatography, affording crude 3 (ca. 90% purity, 166 mg). Purification by normal-phase HPLC gave pure 3 (75 mg). Minor products 4 and 5 were obtained by HPLC separation of the silica gel chromatography fractions.
10. 6) δ: 212.6 (s, C-7), 136.3 (s, C-12), 136.0 (s, C-4), 133.4 (s, C-1), 128.5 (s, C-16), 128.3 (d, C-3), 124.5 (d, C-11), 84.9 (d, C-2), 78.4 (t, C-17), 45.9 (d, C-8), 42.1 (t, C-6), 38.2 (t, C-13), 33.6 (t, C-9), 26.8 (t, C-10), 26.2 (t, C-5), 23.0 (q, C-18), 23.0 (t, C-14), 18.8 (q, C-19), 15.2 (q, C-20), 9.2 (q, C-15). EIMS m/z 302. HREIMS m/z 302.2247 (+0.2 mmu).
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