August 1, 2016 | Megan H. Shaw, Jack Twilton, and David W. C. MacMillan*
Photoredox catalysis has emerged as a powerful strategy in organic chemistry, enabling the activation of small molecules through the conversion of visible light into chemical energy via single-electron transfer with organic substrates. This Perspective highlights the unique ability of photoredox catalysis to expedite the development of new reaction mechanisms, particularly in multicatalytic strategies that facilitate the construction of challenging carbon–carbon and carbon–heteroatom bonds. The article reviews the historical development of photoredox catalysis, from early applications in water splitting and carbon dioxide reduction to its recent impact on organic synthesis. It discusses the mechanisms by which photoredox catalysts convert light into chemical energy, including energy transfer, organometallic excitation, light-induced atom transfer, and photoredox catalysis. The article also explores the utility of photoredox catalysis in amine α-functionalization, redox-neutral transformations, and the combination of photoredox catalysis with other catalytic platforms such as organocatalysis, transition metal catalysis, and Lewis acid catalysis. Additionally, it covers dual photoredox organocatalysis, hydrogen atom transfer, and metallaphotoredox catalysis, emphasizing the breadth of applications and the potential for novel synthetic transformations.Photoredox catalysis has emerged as a powerful strategy in organic chemistry, enabling the activation of small molecules through the conversion of visible light into chemical energy via single-electron transfer with organic substrates. This Perspective highlights the unique ability of photoredox catalysis to expedite the development of new reaction mechanisms, particularly in multicatalytic strategies that facilitate the construction of challenging carbon–carbon and carbon–heteroatom bonds. The article reviews the historical development of photoredox catalysis, from early applications in water splitting and carbon dioxide reduction to its recent impact on organic synthesis. It discusses the mechanisms by which photoredox catalysts convert light into chemical energy, including energy transfer, organometallic excitation, light-induced atom transfer, and photoredox catalysis. The article also explores the utility of photoredox catalysis in amine α-functionalization, redox-neutral transformations, and the combination of photoredox catalysis with other catalytic platforms such as organocatalysis, transition metal catalysis, and Lewis acid catalysis. Additionally, it covers dual photoredox organocatalysis, hydrogen atom transfer, and metallaphotoredox catalysis, emphasizing the breadth of applications and the potential for novel synthetic transformations.