Funded by European Union CIG-CSP3OCF3

Organocatalytic synthesis of fluorine compounds. Development of
new methodologies for the enantioselective introduction of fluorine
building blocks via CH activation of sp3 carbon

 

2. Our Approach

We use Organic Dyes and light to activate inert amine bonds. The mechanism is highlited below.

Rose Bengal iv accepts a photon of green light exciting it to an excited state, this then abstracts an electron from the tetrahydroisoquinoline by way of a single electron transfer process. This forms a Rose Bengal radical anion iv which after oxidation, by molecular oxygen 81, back to the ground state regenerating the catalytic cycle and forming an oxygen radical anion 81 . The tetrahydroisoquinoline radical cation 49 is deprotonated by the oxygen radical anion 81 to form an iminium cation and a hydroperoxide anion 82.

Once we form the iminium cation we plan to add nucleophilic building blocks such as fluoromalonate, 1-fluoro-1-nitro(phenylsulfonyl)methane, or fluoroacetone.

 

 

Publications:

1- “Organocatalytic Cross Dehydrogenative copling for Synthesis of Fluorinated Compounds” Luke Shirley, Victor Ceban, Marta Meazza and Ramon Rios. ChemistrySelect 2016, 1, 13-15.

2- “Organophotocatalytic synthesis of phosphoramidates” Marta Meazza, Agnieszka Kowalczuk, Luke Shirley, Hao Guo* and Ramon Rios*.Adv. Synth. Catal. 2016, 358, 719-723.