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Total Syntheses of ent-Heliespirones A and C

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Figshare2016-02-22 更新2026-04-29 收录
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Stereodivergent total syntheses of ent-heliespirone A and C were both completed in 11 vessels and ∼24% combined overall yield (A + C). These syntheses employed an identical inverse demand Diels–Alder reaction between a surrogate for an extendedly conjugated γ–δ unsaturated ortho-quinone methide and l-lactic-acid-derived exocyclic enol ether. Novel reactions of special note include a diastereoselective reduction of a chroman spiroketal by combination of borontrifluoride etherate and triethyl silane, along with oxidative rupture of a chroman etherial ring into the corresponding p-quinone by argentic oxide (AgO). In addition, an unusual intramolecular etherification of a 3° alcohol caused by cerium ammonium nitrate was observed.

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2016-02-22
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