We show that enantioselective reactions can be induced by the electron spin itself and that it is possible to replace ac onventional enantiopure chemical reagent by spinpolarized electrons that provide the chiral bias for enantioselective reactions.Three examples of enantioselective chemistry resulting from electron-spin polarization are presented. One demonstrates the enantioselective association of ac hiral molecule with an achiral self-assembled monolayer film that is spin-polarized, while the other two show that the chiral bias provided by the electron helicity can drive both reduction and oxidation in enantiospecific electrochemical reactions.Ineach case,the enantioselectivity does not result from enantiospecific interactions of the molecule with the ferromagnetic electrode but from the polarized spin that crosses the interface between the substrate and the molecule.F urthermore,t he direction of the electron-spin polarization defines the handedness of the enantioselectivity.T his work demonstrates an ew mechanism for realizing enantioselective chemistry.

Essential aspects of the chiral induced spin selectivity (CISS) effect and their implications for spin-controlled chemistry and asymmetric electrochemical reactions are described. The generation of oxygen through electrolysis is discussed...

A 7‐pyrrolidino‐7‐benzylamino‐8,8‐dicyanoquinodimethane, PBEDQ, (1), donor–acceptor–modified electrode yields, in the presence of hydroquinone, (2), an anodic photocurrent with quantum efficiency of 1.5%. The PBEDQ‐functionalized electrode yields, in the presence of the electron acceptor diquat, (3), a cathodic photocurrent with a quantum efficiency corresponding to 2.1%. The electron transfer cascades leading to the anodic or cathodic photocurrents in the different systems are discussed. It is further demonstrated that the integration of 1,4‐dihydronicotinamide adenine dinucleotide, NADH, as electron donor, with the PBEDQ‐modified electrode leads to an anodic photocurrent. This allowed the assembly of a photobioelectrochemical integrated electrode composed of the photoactive PBEDQ donor–acceptor compound, NAD+ as cofactor, and the NAD+‐dependent glucose dehydrogenase, GDH. Irradiation of the integrated electrode in the presence of glucose results in the GDH–biocatalyzed oxidation of glucose to gluconic acid with the concomitant generation of NADH that acts as electron donor for the photoactive donor–acceptor PBEDQ units, leading to the generation of steady‐state anodic photocurrent. The photocurrent intensities are controlled by the concentrations of glucose. The integrated PBEDQ/NAD+/GDH electrodes introduces a functional photobioelectrochemical electrode for the detection of glucose, and demonstrates the assembly of a functional photo‐biofuel cell that uses light and a biomass product (glucose) for the generation of electric power.

We show that enantioselective reactions can be induced by the electron spin itself and that it is possible to replace ac onventional enantiopure chemical reagent by spinpolarized electrons that provide the chiral bias for enantioselective reactions.Three examples of enantioselective chemistry resulting from electron-spin polarization are presented. One demonstrates the enantioselective association of ac hiral molecule with an achiral self-assembled monolayer film that is spin-polarized, while the other two show that the chiral bias provided by the electron helicity can drive both reduction and oxidation in enantiospecific electrochemical reactions.Ineach case,the enantioselectivity does not result from enantiospecific interactions of the molecule with the ferromagnetic electrode but from the polarized spin that crosses the interface between the substrate and the molecule.F urthermore,t he direction of the electron-spin polarization defines the handedness of the enantioselectivity.T his work demonstrates an ew mechanism for realizing enantioselective chemistry.

Enantioselective catalytic chiral reactions are important to all aspects of life sciences. Here we present the first utilization of the chiral induced spin selectivity (CISS) effect to form, enantioselectively, sp 3 chiral centers in catalytic reactions, starting from achiral reagents. The enantiomeric symmetry is broken by affecting spin-controlled different reaction dynamics toward each of the enantiomers, using magnetic substrates. Two catalytic reactions are used for this purpose: a sulfide to sulfoxide oxidation and a Diels−Alder cycloaddition reaction, both catalyzed by hematite (Fe 2 O 3 ). The proof of concept was evaluated by circular dichroism measurements and by chiral high-performance liquid chromatography techniques. These results provide direct evidence that the directionality of the electron spin can break enantiomeric symmetry, enabling asymmetric catalysis without using chiral reagents, solvents, or catalysts.