Hock and interrupted Hock reactions: mechanisms, reaction design and synthetic applications – RHOCKI

This project aims at studying the mechanism of the Hock rearrangement, an oxidative cleavage of allylic or benzylic hydroperoxides into carbonyl compounds, and at expending its application scope thanks to a combination of experimental and theoretical studies. This acid-catalyzed rearrangement indeed produces a reactive oxocarbonium intermediate that could be exploited in numerous tandem synthetic methods involving reactions with appropriate nucleophiles, thus interrupting the classical Hock mechanism.

- First development of a methodology of interrupted Hock reaction
- First DFT calculation on this fondamental reaction, showing a phenonium intermediate
- Application to the synthesis of valuable compounds

- Development and scope of the methodology of interrupted Hock reaction
- Further DFT calculation on this fondamental reaction, showing the influence of substituents
- Application to the synthesis of valuable compounds

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This project aims at studying the mechanism of the Hock rearrangement, an oxidative cleavage of allylic or benzylic hydroperoxides into carbonyl compounds, and at expending its application scope in organic synthesis thanks to a combination of experimental and theoretical studies. This acid-catalyzed rearrangement indeed produces a reactive oxocarbonium intermediate that could be exploited in numerous tandem synthetic methods involving reactions with various nucleophiles, thus interrupting the classical Hock mechanism. RHOCKI will thus target three objectives:
1. Demonstration of the mechanism of this reaction and determination of key parameters;
2. Design of new reactions based on interrupted Hock processes, as supported by computation;
3. Applications of Hock and interrupted Hock reactions in synthesis of valuable compounds.
By revisiting the Hock rearrangement, RHOCKI thus proposes an ambitious and eco-compatible strategy for the development of new reactions.