Photochromism

Catalysis

Composite material

Polymer

Enantioselective synthesis

Organic chemistry

Enzyme

Merocyanine

Amphiphile

Compartmentalization (fire protection)

Copolymer

Nanoreactor

Micelle

Aqueous solution

Chemistry

Materials science

Photochemistry

Combinatorial chemistry

Tandem

Journal of the American Chemical Society

This contribution describes an advanced compartmentalized micellar nanoreactor that possesses a reversible photoresponsive feature and its application toward photoregulating reaction pathways for incompatible tandem catalysis under aqueous conditions. The smart nanoreactor is based on multifunctional amphiphilic poly(2-oxazoline)s and covalently cross-linked with spiropyran upon micelle formation in water. It responds to light irradiation in a wavelength-selective manner switching its morphology as confirmed by dynamic light scattering and cryo-transition electron microscopy. The compartmental structure renders distinct nanoconfinements for two incompatible enantioselective transformations: a rhodium-diene complex-catalyzed asymmetric 1,4-addition occurs in the hydrophilic corona, while a Rh-TsDPEN-catalyzed asymmetric transfer hydrogenation proceeds in the hydrophobic core. Control experiments and kinetic studies showed that the gated behavior induced by the phototriggered reversible spiropyran to merocyanin...

Compartmentalization and Photoregulating Pathways for Incompatible Tandem Catalysis