Nucleophilic Activation Strategy in Synergistic Gold-Silicon Catalysis Organo-metallocatalysis

A PhD position is available in one of the research teams of URCOM (Université Le Havre Normandie-ULHN) and is starting in october 2025 with a 3 year duration.

The team has a long-standing interest in cationic chemistry and to a larger extent in electrophilic catalysis. One of its main research topics is now dedicated to the development of organometallic and/or synergistic catalytic strategies involving cationic intermediates or substrates.

Since the early 2000s, gold catalysis has developed considerably, opening up a wide range of new synthetic opportunities in organic chemistry. In this field, our team is interested in developing catalytic methods for the catalytic transfer of alkynes onto highly reactive cationic electrophiles (carbocations, iminium and oxycarbenium derivatives).

The synergistic Au(I)/silicon catalysis strategy at the heart of this project is based on the catalytic activation of alkynylTMS by a cationic gold(I) complex LAuX, allowing the in situ formation by 'aurodesilation' of two key catalytic species: a silylated strong electrophile, TMSX, which, once formed, activates an electrophilic substrate (N,O-acetals, cyclic acetals, glycoside donors, …) to form a cationic intermediate to which the second entity, a gold acetylide, is added.

For each new reaction studied, the challenge is to achieve the optimum catalytic system by choosing the [L ligand + X counterion] pair that provides the right balance between sufficiently rapid aurodesilation to ensure the formation of the two catalytic species involved and the best possible reactivity of the latter. Overall, the project aims to extend the scope of the concept of synergistic gold/silicon catalysis. Specifically, it will focus on the evaluation of new catalytic systems designed to overcome the remaining barriers to the process. These investigations will be carried out as part of the development of novel transformations, including cascade processes, for which current tools are inadequate or inappropriate.

Université Le Havre Normandie (ULHN) - France

Laboratoire URCOM (Unité de Recherche en Chimie Organique et Macromoléculaire) 

M2 research in organic chemistry. He/she should have a solid background in organic synthesis and a good knowledge of the usual characterisation methods (NMR, GC, MS, HPLC, etc.). Previous experience in organometallic catalysis would be welcome. The candidate should have a strong motivation for research, be well organised and able to work independently. Very gool oral and written communications skills are required.