We report an improved synthetic protocol for hydroxymethyl-derivedpolysubstituted furans employing Bi-(III)-catalyzed dehydrative cycloisomerizationof alpha-hydroxy oxetanyl ketones. This procedure provides rapidaccess (within 5 min) to highly substituted furans with exceptionalfunctional group diversity, excellent yields, generality, scalability,and operationally simple reaction conditions. Further, it demonstratedthe utility of this method in the first enantioselective total synthesisof furyl-hydroquinone-derived biologically potent natural productsshikonofurans J, D, E, and C in seven linear steps, starting fromreadily available building blocks of 2,5-dihydroxy acetophenone and3-oxetanone employing chiral-phosphoric acid (TRIP)-catalyzed asymmetricprenylation as a key step to induce the chirality.

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