Related Experiment Video
Updated: May 15, 2025

Facile Preparation of 4-Substituted Quinazoline Derivatives
Published on: February 15, 2016
Total Synthesis of Dactyloquinone A and Spiroetherone A via a Metal-Hydride Hydrogen Atom Transfer (MHAT) Process and
Guillaume Schoenn1, Cyrille Kouklovsky1, Régis Guillot1
1Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Unviversité Paris-Saclay, CNRS, Bâtiment Henri Moissan, 17 Avenue des Sciences, Orsay, 91405, France.
Abstract:
We report the total synthesis of dactyloquinone A and spiroetherone A from a meroterpenoid scaffold obtained by the deconjugative alkylation of a Wieland-Miescher type ketone. For dactyloquinone A, we employed an intramolecular hydrofunctionalisation of the internal trisubstituted alkene with a quinone monoacetal via a metal-hydride hydrogen atom transfer (MHAT) process to form the key C─O bond. For spiroetherone A, we relied on a stereospecific quinol-spiroenedione rearrangement. The initially postulated structure of spiroetherone A was first synthesized, but was found to be different from the natural product. Finally, spiroetherone A was shown to be epimeric at the spirocyclic carbon. This finding was confirmed by total synthesis involving epimerization of the spirocycle via a late-stage singlet oxygen [4+2] cycloaddition to a cyclohexadiene derived from the initial enedione.
Related Concept Videos
Oxidation of Phenols to Quinones
o-hydroxy phenols are oxidized to o-quinones and p-hydroxy phenols to p-quinones. Such redox reactions involve the transfer of two electrons and two protons. The reversible redox...
Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction

