How Robust Is the Reversible Steric Shielding Strategy for Photoswitchable Organocatalysts?

ABSTRACT: A highly appealing strategy to modulate a catalyst's activity and/or selectivity in a dynamic and noninvasive 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

SUBMITTER: Gallarati S 

PROVIDER: S-EPMC9295146 | biostudies-literature | 2022 Jul

REPOSITORIES: biostudies-literature