期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 23, 期 25, 页码 6174-6184出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201604966
关键词
activity control; Michael addition; molecular switches; photochemistry; photoswitchable catalysts
资金
- Netherlands Organization for Scientific Research (NWO-CW)
- Foundation for Fundamental Research on Matter (FOM, a subsidiary of NWO)
- Zernike Institute for Advanced Materials
- Royal Netherlands Academy of Arts and Sciences (KNAW)
- European Research Council [227897]
- Ministry of Education, Culture and Science [024.001.035]
- University of Groningen
The emerging field of artificial photoswitchable catalysis has recently shown striking examples of functional light-responsive systems allowing for dynamic control of activity and selectivity in organocatalysis and metal-catalysed transformations. While our group has already disclosed systems featuring first generation molecular motors as the switchable central core, a design based on second generation molecular motors is lacking. Here, the syntheses of two bifunctionalised molecular switches based on a photoresponsive tetrasubstituted alkene core are reported. They feature a thiourea substituent as hydrogen-donor moiety in the upper half and a basic dimethylamine group in the lower half. This combination of functional groups offers the possibility for application of these molecules in photoswitchable catalytic processes. The light-responsive central cores were synthesized by a Barton-Kellogg coupling of the prefunctionalized upper and lower halves. Derivatization using Buchwald-Hartwig amination and subsequent introduction of the thiourea substituent afforded the target compounds. Control of catalytic activity in the Michael addition reaction between (E)-3-bromo--nitrostyrene and 2,4-pentanedione is achieved upon irradiation of stable-(E) and stable-(Z) isomers of the bifunctional catalyst 1. Both isomers display a decrease in catalytic activity upon irradiation to the metastable state, providing systems with the potential to be applied as ON/OFF catalytic photoswitches.
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