Nickel-Catalyzed Decarboxylative Cross-Coupling of Perfluorobenzoates with Aryl Halides and Sulfonates

Sardzinski, Logan W.; Wertjes, William C.; Schnaith, Abigail; Kalyani, Dipannita

doi:10.1021/acs.orglett.5b00241

Cited by 45 publications

(14 citation statements)

References 51 publications

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“… 22 In light of this, we were surprised to observe that polyfluorinated benzoic acids showed excellent reactivity under these conditions ( 2ac – 2ae ); we are currently studying the reason for this unexpected reactivity. 23 The procedure was also applied to the methylestrone-2-carboxylic acid 1af to provide the corresponding iodide in high yield ( 2af ). 24 In accord with the general trend of reactivity, substrates that do not bear electron-donating substituents were unreactive under these conditions ( 2ag – 2aj ).…”

Section: Resultsmentioning

confidence: 99%

Transition-Metal-Free Decarboxylative Iodination: New Routes for Decarboxylative Oxidative Cross-Couplings

et al. 2017

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Constructing products of high synthetic value from inexpensive and abundant starting materials is of great importance. Aryl iodides are essential building blocks for the synthesis of functional molecules, and efficient methods for their synthesis from chemical feedstocks are highly sought after. Here we report a low-cost decarboxylative iodination that occurs simply from readily available benzoic acids and I2. The reaction is scalable and the scope and robustness of the reaction is thoroughly examined. Mechanistic studies suggest that this reaction does not proceed via a radical mechanism, which is in contrast to classical Hunsdiecker-type decarboxylative halogenations. In addition, DFT studies allow comparisons to be made between our procedure and current transition-metal-catalyzed decarboxylations. The utility of this procedure is demonstrated in its application to oxidative cross-couplings of aromatics via decarboxylative/C–H or double decarboxylative activations that use I2 as the terminal oxidant. This strategy allows the preparation of biaryls previously inaccessible via decarboxylative methods and holds other advantages over existing decarboxylative oxidative couplings, as stoichiometric transition metals are avoided.

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Section: Resultsmentioning

confidence: 99%

Transition-Metal-Free Decarboxylative Iodination: New Routes for Decarboxylative Oxidative Cross-Couplings

et al. 2017

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“…Furthermore, the decarboxylation of 2 a was investigated to gain brief insights to the mechanism of this decarboxylative cross‐coupling (Table ) ,,. Pentafluorobenzene 14 was obtained in 9% yield in c hexane at 170 °C within 16 h while the adding of nickel catalysts like Ni(cod) 2 and NiCl 2 or additives like ZnCl 2 , Ag 2 CO 3 and Cu 2 O gave similar results.…”

Section: Methodsmentioning

confidence: 99%

Ni‐Catalyzed Decarboxylative Cross‐Coupling of Potassium Polyfluorobenzoates with Unactivated Phenol and Phenylmethanol Derivatives

Chen

Qin

et al. 2018

Adv Synth Catal

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A Ni-catalyzed decarboxylative crosscoupling of potassium polyfluorobenzoates with unactivated phenol and phenylmethanol derivatives is described. This novel transformation provides a practical and efficient protocol towards the synthesis of important polyfluorobiaryls and polyfluorinated diarylmethanes, and greatly enlarges the range of electrophiles utilized in decarboxylative coupling. Remarkably, preliminary mechanistic studies indicated the essential role of Zn(OAc) 2 might lie in the enhancement of decarboxylation step.

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“…Spectroscopic data for 3ad match with those previously reported in the literature. 21 2,2′,3,3′,4,5,5′,6,6′-Nonafluoro-1,1′:4′,1″-terphenyl (3ca). Following the general procedure, a white solid in 61% yield (478 mg) was obtained from perfluorodiphenyl (2 mmol, 668 mg) and C 6 H 5 -Bneop (2 mmol, 380 mg).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

NHC Nickel-Catalyzed Suzuki–Miyaura Cross-Coupling Reactions of Aryl Boronate Esters with Perfluorobenzenes

et al. 2016

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An efficient Suzuki-Miyaura cross-coupling reaction of perfluorinated arenes with aryl boronate esters using NHC nickel complexes as catalysts is described. The efficiencies of different boronate esters (p-tolyl-Beg, p-tolyl-Bneop, p-tolyl-Bpin, p-tolyl-Bcat) and the corresponding boronic acid (p-tolyl-B(OH)2) in this type of cross-coupling reaction were evaluated (eg, ethyleneglycolato; neop, neopentylglycolato; pin, pinacolato; cat, catecholato). Aryl-Beg was shown to be the most reactive boronate ester among those studied. The use of CsF as an additive is essential for an efficient reaction of hexafluorobenzene with aryl neopentylglycolboronates.

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Nickel-Catalyzed Decarboxylative Cross-Coupling of Perfluorobenzoates with Aryl Halides and Sulfonates

Cited by 45 publications

References 51 publications

Transition-Metal-Free Decarboxylative Iodination: New Routes for Decarboxylative Oxidative Cross-Couplings

Transition-Metal-Free Decarboxylative Iodination: New Routes for Decarboxylative Oxidative Cross-Couplings

Ni‐Catalyzed Decarboxylative Cross‐Coupling of Potassium Polyfluorobenzoates with Unactivated Phenol and Phenylmethanol Derivatives

NHC Nickel-Catalyzed Suzuki–Miyaura Cross-Coupling Reactions of Aryl Boronate Esters with Perfluorobenzenes

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