One-pot synthesis of (+)-nootkatone via dark singlet oxygenation of valencene: The triple role of the amphiphilic molybdate catalyst - Archive ouverte HAL
Article Dans Une Revue Catalysts Année : 2016

One-pot synthesis of (+)-nootkatone via dark singlet oxygenation of valencene: The triple role of the amphiphilic molybdate catalyst

Résumé

Efficient one-pot catalytic synthesis of (+)-nootkatone was performed from (+)-valencene using only hydrogen peroxide and amphiphilic molybdate ions. The process required no solvent and proceeded in three cascade reactions: (i) singlet oxygenation of valencene according to the ene reaction; (ii) Schenck rearrangement of one hydroperoxide into the secondary β-hydroperoxide; and (iii) dehydration of the hydroperoxide into the desired (+)-nootkatone. The solvent effect on the hydroperoxide rearrangement is herein discussed. The amphiphilic dimethyldioctyl ammonium molybdate, which is also a balanced surfactant, played a triple role in this process, as molybdate ions catalyzed at both Step 1 and Step 3 and it allowed the rapid formation of a three-phase microemulsion system that highly facilitates product recovery. Preparative synthesis of the high added value (+)-nootkatone was thus performed at room temperature with an isolated yield of 46.5%. This is also the first example of a conversion of allylic hydroperoxides into ketones catalyzed by molybdate ions.
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Dates et versions

hal-01462884 , version 1 (12-12-2023)

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B. Hong, R. Lebeuf, S. Delbaere, P.L. Alsters, V. Nardello-Rataj. One-pot synthesis of (+)-nootkatone via dark singlet oxygenation of valencene: The triple role of the amphiphilic molybdate catalyst. Catalysts, 2016, 6, pp.184-1 - 184-11. ⟨10.3390/catal6120184⟩. ⟨hal-01462884⟩

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