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Catalysts 2016, 6(12), 184; doi:10.3390/catal6120184

One-Pot Synthesis of (+)-Nootkatone via Dark Singlet Oxygenation of Valencene: The Triple Role of the Amphiphilic Molybdate Catalyst

1
Université Lille, CNRS, Centrale Lille, ENSCL, Université Artois, UMR 8181-UCCS-Unité de Catalyse et Chimie du Solide, F-59000 Lille, France
2
Université Lille, UDSL, CNRS UMR 8516, F-59006 Lille, France
3
DSM ChemTech R&D B.V., Innovative Synthesis, P.O. Box 18, 6160 MD Geleen, The Netherlands
*
Author to whom correspondence should be addressed.
Academic Editor: Keith Hohn
Received: 16 September 2016 / Revised: 7 November 2016 / Accepted: 18 November 2016 / Published: 26 November 2016
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Abstract

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. View Full-Text
Keywords: (+)-valencene; (+)-nootkatone; molybdate ions; hydrogen peroxide; singlet oxygen; microemulsion (+)-valencene; (+)-nootkatone; molybdate ions; hydrogen peroxide; singlet oxygen; microemulsion
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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MDPI and ACS Style

Hong, B.; Lebeuf, R.; Delbaere, S.; Alsters, P.L.; Nardello-Rataj, V. One-Pot Synthesis of (+)-Nootkatone via Dark Singlet Oxygenation of Valencene: The Triple Role of the Amphiphilic Molybdate Catalyst. Catalysts 2016, 6, 184.

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