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photoredox catalysis
Photoredox catalysis is a branch of catalysis that harnesses the energy of visible light to accelerate a chemical reaction via a single-electron transfer. This area is named as a combination of "photo-" referring to light and redox, a condensed expression for the chemical processes of reduction and oxidation. In particular, photoredox catalysis employs small quantities of a light-sensitive compound that, when excited by light, can mediate the transfer of electrons between chemical compounds that otherwise would not react. Photoredox catalysts are generally drawn from three classes of materials: transition-metal complexes, organic dyes and semiconductors. While each class of materials has advantages, soluble transition-metal complexes are used most often.
Study of this branch of catalysis led to the development of new methods to accomplish known and new chemical transformations. One attraction to the area is that photoredox catalysts are often less toxic than other reagents often used to generate free radicals, such as organotin reagents. Furthermore, while photoredox catalysts generate potent redox agents while exposed to light, they are innocuous under ordinary conditions Thus transition-metal complex photoredox catalysts are in some ways more attractive than stoichiometric redox agents such as quinones. The properties of photoredox catalysts can be modified by changing ligands and the metal, reflecting the somewhat modular nature of the catalyst.
While photoredox catalysis has most often been applied to generate known reactive intermediates in a novel way, the study of this mode of catalysis led to the discovery of new organic reactions, such as the first direct functionalization of the β-arylation of saturated aldehydes. Although the D3-symmetric transition-metal complexes used in many photoredox-catalyzed reactions are chiral, the use of enantioenriched photoredox catalysts led to low levels of enantioselectivity in a photoredox-catalyzed aryl-aryl coupling reaction, suggesting that the chiral nature of these catalysts is not yet a highly effective means of transmitting stereochemical information in photoredox reactions. However, while synthetically useful levels of enantioselectivity have not been achieved using chiral photoredox catalysts alone, optically-active products have been obtained through the synergistic combination of photoredox catalysis with chiral organocatalysts such as secondary amines and Brønsted acids.
== Photochemistry of transition metal photocatalysts ==
The activity of a photoredox catalyst can be described in three steps. First, a molecule of the catalyst in its ground state, where the electrons are distributed among the lowest-energy combination of states, interacts with light and moves into a long-lived excited state, where the electrons are not distributed among the lowest-energy combination of available states. Second, the photoexcited catalyst interacts by an outer sphere electron transfer process to "quench" the excited state and to activate one of the other components of the chemical reaction. Finally, a second single electron transfer occurs to return the catalyst to its original oxidation state and electron arrangement.
抄文引用元・出典: フリー百科事典『 ウィキペディア（Wikipedia）』
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