Doctoral Themes - Proposals

Phosphane-based complexes as sustainable heterogeneous or homogeneous catalysts for environmentally relevant organic transformations (PTADevCat)

Supervisors

M. Fátima C. Guedes da Silva, fatima.guedes@tecnico.ulisboa.pt

Sónia Carabineiro, sonia.carabineiro@fct.unl.pt

Registration Institution

Instituto Superior Técnico (Universidade de Lisboa)

Project description

The project involves the synthesis of phosphanes, their transition-metal (mainly first row) coordination compounds, and application as heterogeneous, supported and/or homogeneous catalysts in industrially relevant transformations.

It aims to derivatize the water-soluble 1,3,5-triaza-7-phosphaadamantane (PTA) in order to obtain families of acylated (AcylPTA) and of N- and P-functionalized PTA derivatives (NDevPTA and PDevPTA, in this order). The number of donor groups (or atoms) in the phosphanes will potentially enable a diversity of structures and/or topologies involving one or more metals, but also the consequent tuning of the catalytic properties of the compounds.

The obtained compounds will be tested as homogeneous, heterogeneous or supported catalysts in selected reactions with recognized industrial significance, for which a continuous search for higher selectivities and yields of products under sustainable conditions is persistent. The following transformations will preferentially be tested in the following catalysis: (i) nitroaldol (Henry) reaction between a nitroalkane and an aldehyde to afford the synthetically useful beta-nitroalkanol; (ii) three-component dipolar (Huisgen) cycloaddition between and alkyne, an organic halide and an azide to produce substituted five-membered heterocycles; (iii) the A3 coupling involving an alkyne, an aldehyde and a secondary amine to produce propargylamines, also known as synthetically versatile.

Keywords

Phosphane / Catalysis / Sustainability

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