August 1, 2016 | Megan H. Shaw, Jack Twilton, and David W. C. MacMillan
Photoredox catalysis has emerged as a powerful strategy in organic chemistry for activating small molecules through the conversion of visible light into chemical energy. This process involves metal complexes and organic dyes that facilitate single-electron transfer with organic substrates, generating reactive intermediates. The unique ability of photoredox catalysis to expedite the development of new reaction mechanisms, particularly in multicatalytic strategies for constructing carbon–carbon and carbon–heteroatom bonds, is highlighted in this Perspective.
Over the past four decades, photoredox catalysis has been applied in areas such as water splitting, carbon dioxide reduction, and solar cell development. However, its potential in organic synthesis has only recently been fully realized. Key factors include the use of accessible metal polypyridyl complexes and organic dyes under mild conditions, enabling the generation of reactive species through single-electron transfer. Visible light, which is not absorbed by common organic molecules, selectively excites the photoredox catalyst, allowing it to act as both an oxidant and reductant. This dual functionality provides a unique reaction environment for organic chemistry.
Recent advances in photoredox catalysis have enabled the development of novel synthetic methodologies. Photoredox catalysts can act as both oxidants and reductants in their excited states, and their ability to convert visible light into significant chemical energy (e.g., the triplet state of Ir(ppy)₃ is 56 kcal mol⁻¹ above the ground state) has broad implications for synthetic transformations. The combination of these capabilities has led to the development of new reaction pathways and has significantly increased the number of publications in the field since the late 2000s.
Photoredox catalysis has been applied to various transformations, including the α-functionalization of amines, redox-neutral transformations, and the development of dual catalytic platforms. These include the use of photoredox catalysis with organocatalysis, transition metal catalysis, and Lewis acid catalysis. For example, the enantioselective α-alkylation of aldehydes using α-bromo carbonyls has been achieved through the combination of enamine and photoredox catalysis. Additionally, the development of redox-neutral α-alkylations of N-arylamines has been demonstrated, with the nucleophilic α-amino radical being trapped directly.
The integration of photoredox catalysis with other catalytic systems has enabled the development of new synthetic strategies, including the use of chiral catalysts and the generation of electrophilic intermediates. These strategies have been applied to a wide range of transformations, including the functionalization of amines, the alkylation of heteroarenes, and the formation of complex molecules through radical–radical coupling. The ability of photoredox catalysis to access previously inaccessible reactions has been demonstrated through the development of newPhotoredox catalysis has emerged as a powerful strategy in organic chemistry for activating small molecules through the conversion of visible light into chemical energy. This process involves metal complexes and organic dyes that facilitate single-electron transfer with organic substrates, generating reactive intermediates. The unique ability of photoredox catalysis to expedite the development of new reaction mechanisms, particularly in multicatalytic strategies for constructing carbon–carbon and carbon–heteroatom bonds, is highlighted in this Perspective.
Over the past four decades, photoredox catalysis has been applied in areas such as water splitting, carbon dioxide reduction, and solar cell development. However, its potential in organic synthesis has only recently been fully realized. Key factors include the use of accessible metal polypyridyl complexes and organic dyes under mild conditions, enabling the generation of reactive species through single-electron transfer. Visible light, which is not absorbed by common organic molecules, selectively excites the photoredox catalyst, allowing it to act as both an oxidant and reductant. This dual functionality provides a unique reaction environment for organic chemistry.
Recent advances in photoredox catalysis have enabled the development of novel synthetic methodologies. Photoredox catalysts can act as both oxidants and reductants in their excited states, and their ability to convert visible light into significant chemical energy (e.g., the triplet state of Ir(ppy)₃ is 56 kcal mol⁻¹ above the ground state) has broad implications for synthetic transformations. The combination of these capabilities has led to the development of new reaction pathways and has significantly increased the number of publications in the field since the late 2000s.
Photoredox catalysis has been applied to various transformations, including the α-functionalization of amines, redox-neutral transformations, and the development of dual catalytic platforms. These include the use of photoredox catalysis with organocatalysis, transition metal catalysis, and Lewis acid catalysis. For example, the enantioselective α-alkylation of aldehydes using α-bromo carbonyls has been achieved through the combination of enamine and photoredox catalysis. Additionally, the development of redox-neutral α-alkylations of N-arylamines has been demonstrated, with the nucleophilic α-amino radical being trapped directly.
The integration of photoredox catalysis with other catalytic systems has enabled the development of new synthetic strategies, including the use of chiral catalysts and the generation of electrophilic intermediates. These strategies have been applied to a wide range of transformations, including the functionalization of amines, the alkylation of heteroarenes, and the formation of complex molecules through radical–radical coupling. The ability of photoredox catalysis to access previously inaccessible reactions has been demonstrated through the development of new