Organic Letters
Letter
and the benzyl group was selectively removed in the presence
of the PMB group with lithium di-tert-butylbiphenylide
(LiDBB)15 (82%). Oxidation (89%) of the resulting alcohol
26 followed by the Takai reaction16 gave vinyl iodide 28 (78%).
In the Takai reaction using THF as a solvent, the product was
obtained as an inseparable mixture of E/Z (ca. 4:1) isomers. On
the other hand, the use of dioxane gave a low yield, albeit with
good selectivity. After an examination of the solvents, the mixed
solvent gave vinyl iodide 28 in good yield and selectivity. The
PMB group was cleaved by DDQ, and the resulting primary
alcohol 29 was oxidized by Dess-Martin periodinane (71% in
two steps). Finally, Pinnick oxidation of aldehyde 30 gave
carboxylic acid 4.
With the two segments in hand, we tried to construct the 18-
membered ring of biselyngbyolide B. First, we used the Stille
coupling reaction between stannane 11 and vinyl iodide 28.
The coupling reaction gave the desired diene, but the diene
moiety was too sensitive to deprotection of the PMB and
TBDPS groups and gave the corresponding seco acid
compound. Thus, we decided to construct the diene moiety
in the final stage.
Experimental procedures, spectroscopic data, and 1H and
AUTHOR INFORMATION
Corresponding Author
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Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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This work was supported by the Suzuken Memorial
Foundation and the Naito Foundation. We thank Sanyo Fine
Co., Ltd. for their gift of chiral trityl glycidyl ether.
REFERENCES
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The esterification reaction between alcohol 3 and carboxylic
acid 4 using the Shiina reagent gave ester 31 (87%)(Scheme 5),
Scheme 5. Total Synthesis of Biselyngbyolide B
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which was cyclized by an intramolecular Stille coupling reaction
under high dilution conditions (1.7 mM in DMF)7 to give
protected biselyngbyolide B 32 (94%). The TBS group was
removed by tetrabutylammonium fluoride with acetic acid to
provide biselyngbyolide B (1) (75%). The spectroscopic data
(1H and 13C NMR, HRMS, and optical rotation) for the
synthetic biselyngbyolide B were fully consistent with those of
the natural product.
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In summary, we have achieved the first synthesis of
biselyngbyolide B, the aglycone of biselyngbyaside (27 linear
steps from commercially available 1,3-propane diol and 11%
overall yield in 20 steps from aldehyde 13 based on the longest
linear sequence).
ASSOCIATED CONTENT
* Supporting Information
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The Supporting Information is available free of charge on the
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