Metallaphotoredox: The Merger of Photoredox and Transition Metal Catalysis

Abstract

The merger of photoredox catalysis with transition metal catalysis, termed metallaphotoredox catalysis, has become a mainstay in synthetic methodology over the past decade. Metallaphotoredox catalysis has combined the unparalleled capacity of transition metal catalysis for bond formation with the broad utility of photoinduced electron- and energy-transfer processes. Photocatalytic substrate activation has allowed the engagement of simple starting materials in metal-mediated bond-forming processes. Moreover, electron or energy transfer directly with key organometallic intermediates has provided novel activation modes entirely complementary to traditional catalytic platforms. This Review details and contextualizes the advancements in molecule construction brought forth by metallaphotocatalysis.

Oxidative Addition of Aryl Halides to a Ni(I)-Bipyridine Complex

“…Nickel catalysis has seen tremendous advances in recent years, resulting in the development of diverse methodologies for the formation of C-C and C-heteroatom bonds (Figure 1A). [1][2][3][4][5][6][7] These catalytic reactions span fields such as Ni/photoredox, Ni/electrocatalysis and cross-electrophile coupling, and are enabled by the facile accessibility of numerous Ni oxidation states. 8 Crucially, this includes not only the common Ni(0) and Ni(II) oxidation states, but also the odd-electron Ni(I) and Ni(III) oxidation states.…”

Photosensitized Nickel Catalysis Enabled Silyl Radical Mediated Direct Activation of Carbamoyl Chlorides to Access (Hetero)aryl Carbamides

“…The constant strive to bring about the state-of-the-art methodologies has invigorated scientists to dig deep into the field of photochemistry. One of the significant patrons to this discipline is photoredox catalysis [11][12][13] . This visible-light-induced activation approach has been found to catalyze an assortment of cross-coupling, hydrogen isotope exchange, and C-H activation reactions.…”

Asymmetric β-arylation of cyclopropanols enabled by photoredox and nickel dual catalysis

“…Over the past decade, photoredox catalysis has become a powerful and reliable tool for developing innovative synthetic methodologies, designing and constructing interesting bioactive molecules and valuable functional materials. 6 In this context, there has been tremendous progress in the area of photoredox dual catalysis with transition metals, 7 Lewis acids, 8 organocatalysts, 9 and eletrocatalysts, 10 providing attractive strategies for the stereoselective and divergent preparation of structurally diverse chiral molecules and pharmacophores. Recently, seminal studies have been disclosed toward the asymmetric β-functionalization of cyclopropanols by exploiting these novel catalytic protocols.…”