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How robust is the reversible steric shielding strategy for photoswitchable organocatalysts?

Simone Gallarati1, Raimon Fabregat1, Veronika Juraskova1, Theo Jaffrelot Inizan1, Clemence Corminboeuf1,2,3*

1 Laboratory for Computational Molecular Design, Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne (EPFL), 1015 Lausanne, Switzerland

2 National Center for Competence in Research – Catalysis (NCCR-Catalysis), École Polytechnique Fédérale de Lausanne (EPFL), 1015 Lausanne, Switzerland

3 National Center for Computational Design and Discovery of Novel Materials (MARVEL), École Polytechnique Fédérale de Lausanne (EPFL), 1015 Lausanne, Switzerland

* Corresponding authors emails: clemence.corminboeuf@epfl.ch
DOI10.24435/materialscloud:jw-sh [version v1]

Publication date: Feb 24, 2022

How to cite this record

Simone Gallarati, Raimon Fabregat, Veronika Juraskova, Theo Jaffrelot Inizan, Clemence Corminboeuf, How robust is the reversible steric shielding strategy for photoswitchable organocatalysts?, Materials Cloud Archive 2022.33 (2022), doi: 10.24435/materialscloud:jw-sh.

Description

A highly appealing strategy to modulate a catalyst's activity and/or selectivity in a dynamic and non-invasive way is to incorporate a photoresponsive unit into a catalytically competent molecule. However, the description of the photoinduced conformational or structural changes that alter the catalyst's intrinsic reactivity is often reduced to a handful of intuitive static representations, which can struggle to capture the complexity of flexible organocatalysts. Here, we show how a comprehensive exploration of the free energy landscape of N-alkylated azobenzene-tethered piperidine catalysts is essential to unravel the conformational characteristics of each configurational state and explain the experimentally observed reactivity trends. Mapping the catalysts’ conformational space highlights the existence of false ON or OFF states that lower their switching ability. Our findings expose the challenges associated with the realisation of reversible steric shielding for the photocontrol of Brønsted basicity of piperidine photoswitchable organocatalysts.

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External references

Journal reference
S. Gallarati, R. Fabregat, V. Juraskova, T. Jaffrelot Inizan, C. Corminboeuf, J. Org. Chem. (2022), Under revision

Keywords

ERC SNSF EPFL Photoswitchable organocatalysis Statistical sampling Reversible steric shielding

Version history:

2022.33 (version v1) [This version] Feb 24, 2022 DOI10.24435/materialscloud:jw-sh