Orange Light-Driven C(sp<sup>2</sup>)–C(sp<sup>3</sup>) Cross-Coupling via Spin-Forbidden Ir(III) Metallaphotoredox Catalysis

Xie, Katherine A.; Bednarova, Eva; Joe, Candice L.; Lin, Chenxi; Sherwood, Trevor C.; Simmons, Eric M.; Lainhart, Brendan C.; Rovis, Tomislav

doi:10.1021/jacs.3c06285

Cited by 18 publications

(1 citation statement)

References 45 publications

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“… 43 In addition to osmium-based complexes, the Rovis group recently developed a series of Ir( iii ) photocatalysts that could undergo spin-forbidden excitation. 44 This suggests a broad range of applications for this approach in various heavy metal complexes.…”

Section: Improved Light Absorptionmentioning

confidence: 99%

Improved transition metal photosensitizers to drive advances in photocatalysis

Kim,

Dang,

Teets

2024

Chem. Sci.

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Section: Improved Light Absorptionmentioning

confidence: 99%

Improved transition metal photosensitizers to drive advances in photocatalysis

Kim,

Dang,

Teets

2024

Chem. Sci.

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Divergent Photosensitizer Controlled Reactions of 4‐Hydroxycoumarins and Unactivated Olefins: Hydroarylation and Subsequent [2+2] Cycloaddition

Chang,

Pang,

2023

Angewandte Chemie

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Herein, we report a photoinduced approach for hydroarylation of unactivated olefins using 4‐hydroxycoumarins as the arylating reagent. Key to the success of this reaction is the conversion of nucleophilic 4‐hydroxycoumarins into electrophilic carbon radicals via photocatalytic arene oxidation, which not only circumvents the polarity‐mismatch issue encountered under ionic conditions but also accommodates a broad substrate scope and inhibits side reactions that were previously observed. Moreover, divergent reactivity was achieved by changing the photocatalyst, enabling a subsequent [2+2] cycloaddition to deliver cyclobutane‐fused pentacyclic products that are otherwise challenging to access in high yields and with high diastereoselectivity. Mechanistic studies have elucidated the mechanism of the reactions and the origin of the divergent reactivity.

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Graphitisches Kohlenstoffnitrid als Photokatalysator für die decarboxylative C(sp²)−C(sp³) Kupplung mittels Nickelkatalyse

Lukas,

Findlay,

Fillols

et al. 2024

Angewandte Chemie

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The development of robust and reliable methods for the construction of C(sp2)–C(sp3) bonds is vital for accessing an increased array of structurally diverse scaffolds in drug discovery and development campaigns. While significant advances towards this goal have been achieved using metallaphotoredox chemistry, many of these methods utilise photocatalysts based on precious‐metals due to their efficient redox processes and tuneable properties. However, due to the cost, scarcity, and toxicity of these metals, the search for suitable replacements should be a priority. Here, we show the use of commercially available heterogeneous semiconductor graphitic carbon nitride (gCN) as a photocatalyst, combined with nickel catalysis, for the cross‐coupling between aryl halide and carboxylic acid coupling partners. gCN has been shown to engage in single‐electron‐transfer (SET) and energy‐transfer (EnT) processes for the formation of C–X bonds, and in this manuscript we overcome previous limitations to furnish C–C over C–O bonds using carboxylic acids. A broad scope of both aryl halides and carboxylic acids is presented, and recycling of the photocatalyst demonstrated. The mechanism of the reaction is also investigated.

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Orange Light-Driven C(sp²)–C(sp³) Cross-Coupling via Spin-Forbidden Ir(III) Metallaphotoredox Catalysis

Cited by 18 publications

References 45 publications

Improved transition metal photosensitizers to drive advances in photocatalysis

Improved transition metal photosensitizers to drive advances in photocatalysis

Divergent Photosensitizer Controlled Reactions of 4‐Hydroxycoumarins and Unactivated Olefins: Hydroarylation and Subsequent [2+2] Cycloaddition

Graphitisches Kohlenstoffnitrid als Photokatalysator für die decarboxylative C(sp²)−C(sp³) Kupplung mittels Nickelkatalyse

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Orange Light-Driven C(sp2)–C(sp3) Cross-Coupling via Spin-Forbidden Ir(III) Metallaphotoredox Catalysis

Cited by 18 publications

References 45 publications

Improved transition metal photosensitizers to drive advances in photocatalysis

Improved transition metal photosensitizers to drive advances in photocatalysis

Divergent Photosensitizer Controlled Reactions of 4‐Hydroxycoumarins and Unactivated Olefins: Hydroarylation and Subsequent [2+2] Cycloaddition

Graphitisches Kohlenstoffnitrid als Photokatalysator für die decarboxylative C(sp2)−C(sp3) Kupplung mittels Nickelkatalyse

Contact Info

Product

Resources

About

Orange Light-Driven C(sp²)–C(sp³) Cross-Coupling via Spin-Forbidden Ir(III) Metallaphotoredox Catalysis

Graphitisches Kohlenstoffnitrid als Photokatalysator für die decarboxylative C(sp²)−C(sp³) Kupplung mittels Nickelkatalyse