Abstract
δ-d -Gluconolactone was carbocyclized
into an EOM-protected cyclohexenone in four steps involving perethoxymethylation,
phosphonate anion addition, reduction, and oxidation with concomitant
Horner-Wadsworth-Emmons alkenation. The stable key
enone was efficiently transformed into gabosine I (five steps with
65% overall yield from δ-d -gluconolactone),
streptol (six steps, 54% overall yield), 7-O -acetyl-streptol (seven steps, 42% overall
yield), 1-epi -streptol (six steps, 49% overall
yield), gabosine K (seven steps, 40% overall yield), and
carba-α-d -glucopyranose (seven
steps, 47% overall yield). The present chemical syntheses, from
commercially available δ-d -gluconolactone,
provide the highest overall yields of these molecules to date.
Key words
carbasugars - carbohydrates - stereoselective
synthesis - Wittig reaction - natural products
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