Elucidating electron-transfer events in polypyridine nickel complexes for reductive coupling reactions

Day, Craig S.; Rentería-Gómez, Ángel; Ton, Stephanie J.; Gogoi, Achyut Ranjan; Gutiérrez, Osvaldo; Martı́n, Rubén

doi:10.1038/s41929-023-00925-4

Cited by 69 publications

(59 citation statements)

References 48 publications

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“…Additives have been shown to have a significant impact on Ni-catalyzed coupling reactions. − Therefore, we surveyed inorganic and organic additives in the presence and absence of LiCl (Figure A, entry 4) . We saw an increase in performance to 71% yield when 1.5 equiv of phthalimide 4 was added to the reaction .…”

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confidence: 98%

“…The possibility of 4 facilitating decarbonylation was evaluated, but DFT simulations showed comparable decarbonylation rates for Ni-glutarimide and Ni-phthalimide complexes (Figures S47 and S48). Instead, 4 may play a role in the prevention of unproductive Ni oligomerization 87,89,94,95 or the formation of off-cycle N-acyl-imide Ni complexes. 89,96 On the basis of literature precedent, 59,97,98 mechanistic studies, and additional DFT calculations (see the Supporting Information), we propose a possible reaction pathway (Figure 6C).…”

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confidence: 99%

“…Instead, 4 may play a role in the prevention of unproductive Ni oligomerization 87,89,94,95 or the formation of off-cycle N-acyl-imide Ni complexes. 89,96 On the basis of literature precedent, 59,97,98 mechanistic studies, and additional DFT calculations (see the Supporting Information), we propose a possible reaction pathway (Figure 6C). Oxidative addition of 1 to Ni(0) I generates Ni(II) complex II, which undergoes decarbonylation to III.…”

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confidence: 99%

“…To increase the selectivity for C–C product in such pairs, 30 was subjected to coupling with 2 in the presence of various metal salt additives selected to promote decarbonylation (Table S9). We identified 0.5 equiv of RuCl 3 to be optimal and applied these conditions to the selective coupling of naphthyl ( 31 and 33 ) and quinoline ( 34 ) derivatives (Figure A).…”

mentioning

confidence: 99%

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Formal Cross-Coupling of Amines and Carboxylic Acids to Form sp³–sp² Carbon–Carbon Bonds

et al. 2023

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Amines and carboxylic acids are abundant synthetic building blocks that are classically united to form an amide bond. To access new pockets of chemical space, we are interested in the development of amine–acid coupling reactions that complement the amide coupling. In particular, the formation of carbon–carbon bonds by formal deamination and decarboxylation would be an impactful addition to the synthesis toolbox. Here, we report a formal cross-coupling of alkyl amines and aryl carboxylic acids to form C(sp3)–C(sp2) bonds following preactivation of the amine–acid building blocks as a pyridinium salt and N-acyl-glutarimide, respectively. Under nickel-catalyzed reductive cross-coupling conditions, a diversity of simple and complex substrates are united in good to excellent yield, and numerous pharmaceuticals are successfully diversified. High-throughput experimentation was leveraged in the development of the reaction and the discovery of performance-enhancing additives such as phthalimide, RuCl3, and GaCl3. Mechanistic investigations suggest phthalimide may play a role in stabilizing productive Ni complexes rather than being involved in oxidative addition of the N-acyl-imide and that RuCl3 supports the decarbonylation event, thereby improving reaction selectivity.

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Formal Cross-Coupling of Amines and Carboxylic Acids to Form sp³–sp² Carbon–Carbon Bonds

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“…56 Reductive elimination then delivers the cross-coupled product and singleelectron reduction from Zn turns over the catalyst. Additional studies are required to obtain a more complete mechanics picture including potential disproportionation/comproportionation step, [57][58][59][60][61] off-cycle intermediates, 62,63 or sensitization of Ni species 48,[64][65][66] In summary, we have developed a mild and atom-economic C-N activation strategy relying on SuFEx click chemistry combined with the aza-Ramberg-Bäcklund reaction. This sequence affords an efficient access to diazene molecules, which can be fragmented under blue light with a photocatalyst to form a radical pair.…”

Section: Table 2 Scope Of the Deaminative Ni-catalyzed Arylationmentioning

confidence: 99%

Harnessing Sulfur(VI) Fluoride Exchange Click Chemistry and Photocatalysis for Deaminative Benzylic Arylation

Chattapadhyay

Aydogan

Doktor

et al. 2023

Preprint

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While among the most common functional handles present in organic molecules, amines are a widely underutilized linchpin for C–C bond formation. To facilitate C–N bond cleavage, large activating groups are typically used but result in the generation of stoichiometric amounts of organic waste. Herein, we report an atom-economic activation of benzylic primary amines relying on the Sulfur Fluoride Exchange (SuFEx) click chemistry and the aza-Ramberg-Bäcklund reaction. This two-step sequence allows the efficient generation of 1,2-dialkyldiazenes from primary amines via loss of SO2. Excitation of the diazenes with blue light and an Ir photocatalyst affords radical pairs upon expulsion of N2, which can be coaxed into the formation of C(sp3)–C(sp2) bonds upon diffusion and capture by a Ni catalyst. This unique arylative strategy relying on a trace-less click approach was harnessed in a variety of examples and its mechanism was investigated.

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Electroactive Polymers for On‐Demand Drug Release

Alkahtani,

Elbadawi,

Chapman

et al. 2023

Adv Healthcare Materials

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Conductive materials have played a significant role in advancing society into the digital era. Such materials are able to harness the power of electricity and are used to control many aspects of our daily lives. Conductive polymers (CPs) are an emerging group of polymers that possess metal‐like conductivity yet retain desirable polymeric features, such as processability, mechanical properties and biodegradability. Upon receiving an electrical stimulus, CPs can be tailored to achieve a number of responses, such as harvesting energy, biosensing and stimulating tissue growth. The recent FDA approval of a CP‐based material for a medical device has invigorated their research in healthcare, including as biosensors, tissue engineering grafts and implants. In drug delivery, CPs can act as electrical switches, drug release is achieved at a flick of a switch, thereby providing unprecedented control over drug release. In this review, recent developments in CP as electro‐active polymers for voltage‐stimuli responsive drug delivery systems are evaluated. The review demonstrates the distinct drug release profiles achieved by electro‐active formulations, and both the precision and ease of stimuli response. This level of dynamism promises to yield “smart medicines” and warrants further research. The review concludes by providing an outlook to electro‐active formulations in drug delivery and highlighting their integral roles in healthcare IoT.This article is protected by copyright. All rights reserved

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Elucidating electron-transfer events in polypyridine nickel complexes for reductive coupling reactions

Cited by 69 publications

References 48 publications

Formal Cross-Coupling of Amines and Carboxylic Acids to Form sp³–sp² Carbon–Carbon Bonds

Formal Cross-Coupling of Amines and Carboxylic Acids to Form sp³–sp² Carbon–Carbon Bonds

Harnessing Sulfur(VI) Fluoride Exchange Click Chemistry and Photocatalysis for Deaminative Benzylic Arylation

Electroactive Polymers for On‐Demand Drug Release

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Elucidating electron-transfer events in polypyridine nickel complexes for reductive coupling reactions

Cited by 69 publications

References 48 publications

Formal Cross-Coupling of Amines and Carboxylic Acids to Form sp3–sp2 Carbon–Carbon Bonds

Formal Cross-Coupling of Amines and Carboxylic Acids to Form sp3–sp2 Carbon–Carbon Bonds

Harnessing Sulfur(VI) Fluoride Exchange Click Chemistry and Photocatalysis for Deaminative Benzylic Arylation

Electroactive Polymers for On‐Demand Drug Release

Contact Info

Product

Resources

About

Formal Cross-Coupling of Amines and Carboxylic Acids to Form sp³–sp² Carbon–Carbon Bonds

Formal Cross-Coupling of Amines and Carboxylic Acids to Form sp³–sp² Carbon–Carbon Bonds