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Review
. 2022 Jan 26;122(2):1485-1542.
doi: 10.1021/acs.chemrev.1c00383. Epub 2021 Nov 18.

Metallaphotoredox: The Merger of Photoredox and Transition Metal Catalysis

Amy Y Chan  1 , Ian B Perry  1 , Noah B Bissonnette  1 , Benito F Buksh  1 , Grant A Edwards  1 , Lucas I Frye  1 , Olivia L Garry  1 , Marissa N Lavagnino  1 , Beryl X Li  1 , Yufan Liang  1 , Edna Mao  1 , Agustin Millet  1 , James V Oakley  1 , Nicholas L Reed  1 , Holt A Sakai  1 , Ciaran P Seath  1 , David W C MacMillan  1
Affiliations
Review

Metallaphotoredox: The Merger of Photoredox and Transition Metal Catalysis

Amy Y Chan et al. Chem Rev. .

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.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1.
Scheme 1.. Merger of Photoredox and Transition Metal Catalysis
Scheme 2.
Scheme 2.. Nickel-Catalyzed Decarboxylative Arylation
Scheme 3.
Scheme 3.. Decarboxylative Transformations
Scheme 4.
Scheme 4.. Photoredox Organoboron Cross-Coupling
Scheme 5.
Scheme 5.. Deoxygenative Cross-Couplings
Scheme 6.
Scheme 6.. Other Radical Precursors
Scheme 7.
Scheme 7.. Oxidation Deprotonation C−H Cross-Coupling
Scheme 8.
Scheme 8.. Triple Catalytic C−H Arylation
Scheme 9.
Scheme 9.. Halogen Atom C−H Arylation
Scheme 10.
Scheme 10.. HAT Catalyst-Mediated C−H Cross-Coupling
Scheme 11.
Scheme 11.. Mechanism of Silyl-Radical-Mediated Cross-Electrophile Coupling
Scheme 12.
Scheme 12.. Silyl Radical-Mediated Nickel Metallaphotoredox Transformations
Scheme 13.
Scheme 13.. Nickel- and Photoredox-Catalyzed Etherification
Scheme 14.
Scheme 14.. Energy-Transfer C−O Coupling
Scheme 15.
Scheme 15.. Early Developments in Metallaphotoredox Amination
Scheme 16.
Scheme 16.. Energy Transfer in Metallaphotocatalytic C−N Cross-Coupling
Scheme 17.
Scheme 17.. Other Heteroatomic Nucleophiles in Nickel Metallaphotocatalysis
Scheme 18.
Scheme 18.. Three-Component Coupling via Nickel Metallaphotoredox Catalysis
Scheme 19.
Scheme 19.. Intramolecular Olefin Difunctionalization
Scheme 20.
Scheme 20.. Copper- and Photoredox-Catalyzed Perfluoroalkylation
Scheme 21.
Scheme 21.. Photoredox Trifluoromethylation
Scheme 22.
Scheme 22.. C−H Alkynylation via Copper Metallaphotoredox Catalysis
Scheme 23.
Scheme 23.. Copper Metallaphotoredox Decarboxylative Alkynylation
Scheme 24.
Scheme 24.. Evidence for Inner-Sphere Electrophile Activation by Reiser and Co-workers
Scheme 25.
Scheme 25.. Iodoperfluoroalkylation of Olefins and Alkynes
Scheme 26.
Scheme 26.. Intramolecular Halofunctionalization of Olefins
Scheme 27.
Scheme 27.. Dual-Catalytic Alkyne Difunctionalization by Xia and Co-workers
Scheme 28.
Scheme 28.. Dual-Catalytic Oxidative Sulfonylation of Naphthalenes
Scheme 29.
Scheme 29.. Evidence for a Radical Mechanism in Photoinduced Ullman Coupling
Scheme 30.
Scheme 30.. Mechanism of the Photoinduced Ullman Coupling
Scheme 31.
Scheme 31.. Carbamate Alkylation with Dual Copper Catalytic System
Scheme 32.
Scheme 32.. Synthesis of Protected Primary Amines by Decarboxylative Amination
Scheme 33.
Scheme 33.. Photoredox-Assisted Chan−Lam Coupling
Scheme 34.
Scheme 34.. Dual-Catalytic Decarboxylative Amination of N-Heterocycles
Scheme 35.
Scheme 35.. Metallaphotocatalytic Ullman−Goldberg Coupling Enabled by Halogen Abstraction−Radical Capture
Scheme 36.
Scheme 36.. Palladium and Photoredox-catalyzed C−H Arylation
Scheme 37.
Scheme 37.. Palladium Metallaphotocatalytic C−H Acylation
Scheme 38.
Scheme 38.. Decarboxylative ortho-Acylation of Acetanilides
Scheme 39.
Scheme 39.. Cis-Selective Decarboxylative Alkenylation
Scheme 40.
Scheme 40.. Photoredox-Assisted Decarboxylative Allylation
Scheme 41.
Scheme 41.. Mechanism of Decarboxylation of Less Stabilized Radicals
Scheme 42.
Scheme 42.. Dual-Catalytic Enantioselective Allylation
Scheme 43.
Scheme 43.. Oxidative Carbonylation of Enamides by Dual Palladium and Photoredox Catalysis
Scheme 44.
Scheme 44.. Early Gold Metallaphotocatalysis Reported by Glorius and Coworkers
Scheme 45.
Scheme 45.. Proposed Mechanism of the Gold Metallaphotocatalytic Olefin Oxyarylation
Scheme 46.
Scheme 46.. Arylative Ring Expansion via Gold Metallaphotoredox
Scheme 47.
Scheme 47.. Dual Gold- and Photoredox-Catalyzed Alkynylations
Scheme 48.
Scheme 48.. Arylative Meyer−Schuster Rearrangements
Scheme 49.
Scheme 49.. Photosensitizer-Mediated Electrophile Activation by Gold
Scheme 50.
Scheme 50.. Carbocyclization by Gold Metallaphotoredox Catalysis
Scheme 51.
Scheme 51.. Gold Metallaphotocatalytic Biaryl Synthesis
Scheme 52.
Scheme 52.. Gold and Copper Metallaphotocatalytic Biaryl Synthesis
Scheme 53.
Scheme 53.. Photocatalytic Cobalt-Mediated Cross-Coupling Hydrogen Evolution
Scheme 54.
Scheme 54.. Triply Catalytic Enantioselective Alkylation of Ketones
Scheme 55.
Scheme 55.. Photoinduced Heck Alkylation of Olefins by Cobalt Metallaphotocatalysis
Scheme 56.
Scheme 56.. Benzene Functionalization by Cobalt and Photoredox Co-catalysis
Scheme 57.
Scheme 57.. Dehydrogenative Dual-Catalytic Heterocycle Synthesis
Scheme 58.
Scheme 58.. Dual-Catalytic Dehydrogenations
Scheme 59.
Scheme 59.. Hydroaminoalkylation of 1,3-Dienes
Scheme 60.
Scheme 60.. Titanium Metallaphotocatalytic Spirocyclization
Scheme 61.
Scheme 61.. Photoredox Aldehyde Allylation by Dual Chromium and Photoredox Catalysis
Scheme 62.
Scheme 62.. Rhodium Metallaphotoredox Catalysis
Scheme 63.
Scheme 63.. Ruthenium-Photocatalyzed Meta-Selective Arene Alkylation
Scheme 64.
Scheme 64.. Carbon Dioxide Reduction to Methane by Dual Iron Photocatalysis
Scheme 65.
Scheme 65.. Manganese Metallaphotoredox Catalysis
See this image and copyright information in PMC

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