DS10 - Défi des autres savoirs

Spatially encoded NMR spectroscopy of organic reactions – SENSOR

Submission summary

Monitoring strategies are essential to characterise, understand and eventually control chemical reactions. Nuclear magnetic resonance spectroscopy (NMR) is an unrivalled tool for the structural analysis of small organic molecules, which is also applicable to in situ, real-time monitoring. Multidimensional (ND) NMR spectra, on which structure elucidation typically relies, would in principle be particularly useful for the study of complex reacting mixtures. For systems that evolve on time scales of minutes or faster, however, ND NMR experiments are not applicable in their conventional form. This limitation can be overcome by the use of spatial encoding (SPEN), which consists of recording several sub-experiments in parallel from different regions of the sample, and results in accelerations of ND NMR acquisitions by several orders of magnitude.

The SENSOR project aims at developing advanced NMR monitoring strategies for organic reactions, based on spatial encoding, and use them for the analysis of organocatalytic and multi-component reactions. We will first develop ultrafast 2D NMR methods that are optimised for the analysis of complex reacting mixtures. Specifically, we will exploit the concept of diffusion-ordered spectroscopy and multiple-quantum NMR, which have clear benefits for mixtures but have been very little explored in SPEN experiments. We will then develop SPEN NMR monitoring protocols using either a classic NMR tube, or online monitoring with a recently introduced “flow-tube” approach, which broadens the scope of reactions that may be studied and improves the control of reaction conditions. This will involve both experimental optimisation and the development of novel pulse sequences. Finally we will exploit the resulting methodology to analyse organocatalytic and multicomponent reactions developed at the ICSN, for which key mechanistic questions remain. Specifically, we will consider phosphoric-acid-catalysed cycloadditions and the three-component enantioselective Povarov reaction.

The project will be carried out at the Institute of Natural Product Chemistry (ICSN), which hosts research groups in both analytical chemistry and organic synthesis. The coordinator has recently initiated a new line of research at the ICSN, on NMR methods development for analytical applications. The SENSOR project will strengthen this ongoing effort and make it possible to start new applications on mechanistic studies of organic reactions. The SENSOR team has a strong expertise in NMR methods development and the analysis of organic molecules. The coordinator has also demonstrated his ability to lead independent research projects and supervise Ph.D. students.

The outcome of the SENSOR project will take multiple forms. The project addresses several bottlenecks in reaction monitoring and magnetic resonance, and will have scientific impact in physical chemistry, analytical chemistry and chemical synthesis. All the methods developed throughout the project will be made available to the community in the form of downloadable protocols. These methods will also be available through the user facility at the ICSN, which is accessible to users from both academia and the private sector. Mechanistic insight will be obtained for organocatalytic and multi-component reactions, which will result in the design of new reactions or of improved, enantioselective versions of existing reactions. Beyond these initial demonstrations, the tools developed will be suitable for a broad range of applications of reaction monitoring and NMR spectroscopy.

Project coordination

Jean-Nicolas DUMEZ (CEISAM)

The author of this summary is the project coordinator, who is responsible for the content of this summary. The ANR declines any responsibility as for its contents.

Partner

CEISAM CEISAM
ICSN CNRS IDF SUD Institut de chimie des substances naturelles

Help of the ANR 293,373 euros
Beginning and duration of the scientific project: - 48 Months

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