Photoswitchable interlocked thiodiglycolamide as a cocatalyst of a chalcogeno-Baylis-Hillman reactionElectronic supplementary information (ESI) available: Experimental procedures, spectroscopic and mass spectrometry data for all of the new compounds, and the full crystallographic details of 3a. CCDC 1532346. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc00724h

• Main Authors: Martinez-Cuezva, Alberto, Saura-Sanmartin, Adrian, Nicolas-Garcia, Tomas, Navarro, Cristian, Orenes, Raul-Angel, Alajarin, Mateo, Berna, Jose
• Format: Article
• Language: English
• ISSN: 2041-6520; 2041-6539
• DOI: 10.1039/c7sc00724h

En route to a photoswitchable interlocked catalyst we have proved the ability of thiodiglycolamide to act as a template in the formation of hydrogen-bonded [2]rotaxanes. X-ray diffraction studies reveal the shielding of the sulfide atom by the macrocycle. A series of molecular shuttles are described as having an isomerizable fumaramide and thiodiglycolamide binding sites for controlling the relative ring position at will. By employing these systems as photoregulated catalysts, the TiCl 4 -mediated chalcogeno-Morita-Baylis-Hillman reaction is tested. In the presence of the maleamide shuttle, in which the sulfide function is encapsulated by the macrocycle, a complete loss in control of the geometry of the produced aldol is observed. The E -aldol adduct is predominantly obtained when the photoisomerized fumaramide shuttle, in which the sulfide function is exposed, is used. The sulfur-based template of light-driven molecular shuttles is able to modulate its catalytic activity in a diastereoselective chalcogeno-Baylis-Hillman reaction.