Formation and reactions of monovalent carbon intermediates.  I.  Photolysis of diethyl mercuribisdiazoacetate

Minh, Thap Do; Gunning, H. E.; Strausz, O. P.

doi:10.1021/ja01001a084

Cited by 54 publications

(6 citation statements)

References 1 publication

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Section: Late-stage Aromatic C(sp2)–h Functionalizationmentioning

confidence: 99%

“…Compared to other carbon species lacking one or more valence electrons, carbocations, carbanions, radicals, and carbenes, carbynes, species bearing a monovalent carbon with three nonbonded electrons, are relatively unexplored reactive intermediates. 285 Despite their indomitable reactivity, carbynes can sequentially form three new bonds, therefore offering an "assembly point" disconnection to quaternary centers. Suero and co-workers designed a novel hypervalent iodine precursors (75.1) that can successfully deliver diazomethyl radical 75.5 under photoredox conditions, to be coupled with (hetero)arene substrates (75.2) (Scheme 75A).…”

Section: Miscellaneousmentioning

confidence: 99%

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Photocatalytic Late-Stage C–H Functionalization

et al. 2023

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The emergence of modern photocatalysis, characterized by mildness and selectivity, has significantly spurred innovative late-stage C–H functionalization approaches that make use of low energy photons as a controllable energy source. Compared to traditional late-stage functionalization strategies, photocatalysis paves the way toward complementary and/or previously unattainable regio- and chemoselectivities. Merging the compelling benefits of photocatalysis with the late-stage functionalization workflow offers a potentially unmatched arsenal to tackle drug development campaigns and beyond. This Review highlights the photocatalytic late-stage C–H functionalization strategies of small-molecule drugs, agrochemicals, and natural products, classified according to the targeted C–H bond and the newly formed one. Emphasis is devoted to identifying, describing, and comparing the main mechanistic scenarios. The Review draws a critical comparison between established ionic chemistry and photocatalyzed radical-based manifolds. The Review aims to establish the current state-of-the-art and illustrate the key unsolved challenges to be addressed in the future. The authors aim to introduce the general readership to the main approaches toward photocatalytic late-stage C–H functionalization, and specialist practitioners to the critical evaluation of the current methodologies, potential for improvement, and future uncharted directions.

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Section: Late-stage Aromatic C(sp2)–h Functionalizationmentioning

confidence: 99%

Section: Miscellaneousmentioning

confidence: 99%

Photocatalytic Late-Stage C–H Functionalization

et al. 2023

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“…Carbyne, the unique yet much unexplored reactive intermediate of carbon species, 16–18 lays the foundation for the generation of 1D sp-carbon linear chains, mostly exhibiting closer similarity with graphene and diamonds. 19 Typically, the design of carbyne nanochains requires precise control over reaction conditions, 19–21 where its formation is assisted via the support of a metal 19,22 or metal complexes 21 in an aqueous solution.…”

Section: Introductionmentioning

confidence: 99%

Unravelling the formation of carbyne nanocrystals from graphene nanoconstrictions through the hydrothermal treatment of agro-industrial waste molasses

Jeevanandham,

Kochhar,

Agrawal

et al. 2024

Nanoscale Adv.

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“…In 1967, Strausz first reported that Hg{C(=N 2 )CO 2 Et} 2 could produce free carbyne radicals [:C(•)-R] under UV-Vis irradiation, this carbyne species feature with dual radical and carbene behaviour, such as Csp 3 -H carbenoid insertion and carbene-alkene [1 + 2] cycloaddition (Fig. 1a-I) 15 . Since then, the exploration of alternative carbyne precursors has always kept going forward by chemists.…”

Section: Introductionmentioning

confidence: 99%

Hydroxyl-Diazomethylation of Alkenes via Photoredox Catalysis

Zeng,

Zheng,

Chen

et al. 2023

Preprint

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α-Diazoesters belong to significantly important carbenoid precursors in synthetic chemistry, diazomethylation-based difunctionalization of alkenes is highly valuable but remain nontrivial. Herein, we reported a general and modular approach for the direct 1,2-hydroxyl-diazomethylation of alkenes through visible-light photoredox catalysis. This process exploits photocatalyzed strategy to convert alkenes to γ-hydroxyl-α-diazoesters using α-diazo iodonium salts as carbyne precursors, featuring wide substrate tolerance and broad late-stage diversiﬁcations. Mechanistic studies suggest that the formation of γ-carbocation-tethered α-diazoesters plays a crucial role in trapping H2O to allow for this transformation.

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Formation and reactions of monovalent carbon intermediates. I. Photolysis of diethyl mercuribisdiazoacetate

Cited by 54 publications

References 1 publication

Photocatalytic Late-Stage C–H Functionalization

Photocatalytic Late-Stage C–H Functionalization

Unravelling the formation of carbyne nanocrystals from graphene nanoconstrictions through the hydrothermal treatment of agro-industrial waste molasses

Hydroxyl-Diazomethylation of Alkenes via Photoredox Catalysis

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