Decarboxylative trifluoromethylation of aryl halides using well-defined copper–trifluoroacetate and –chlorodifluoroacetate precursors

McReynolds, Kristen A.; Lewis, Robert S.; Ackerman, Laura K. G.; Dubinina, Galyna G.; Brennessel, William W.; Vicic, David A.

doi:10.1016/j.jfluchem.2010.04.005

Cited by 93 publications

(55 citation statements)

References 37 publications

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“…Importantly, similarly low reactivity has been reported in the literature for other (L~L)Pd II (Aryl)(CF 3 ) complexes (L~L = diphenylphosphinoethane, diphenylphosphinopropane, and diphenylphosphinobenzene). 24a,b As discussed above, the only demonstrated examples of Aryl–CF 3 bond-forming reductive elimination from Pd II require relatively high temperatures (80 °C) and specialized phosphine ligands. 14,15a …”

Section: Resultsmentioning

confidence: 99%

“…4,13 The vast majority of known Pd II (Aryl)(CF 3 ) complexes are inert to Aryl–CF 3 coupling at temperatures as high as 150 °C. 24,21 …”

Section: Introductionmentioning

confidence: 99%

“…This hypothesis is predicated on literature reports showing that Pd IV complexes participate in numerous carbon-heteroatom bond-forming reductive elimination reactions that remain challenging at Pd II centers. 22,23 A key advantage of this approach would be that Pd IV intermediate A could potentially be accessed using nucleophilic (CF 3 − ) 24 , electrophilic (CF 3 + ) 25 , or free-radical (CF 3 ·) 26 based trifluoromethylating reagents.…”

Section: Introductionmentioning

confidence: 99%

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Mechanistic and Computational Studies of Oxidatively-Induced Aryl−CF₃ Bond-Formation at Pd: Rational Design of Room Temperature Aryl Trifluoromethylation

et al. 2011

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This article describes the rational design of 1st generation systems for oxidatively-induced Aryl–CF3 bond-forming reductive elimination from PdII. Treatment of (dtbpy)PdII(Aryl)(CF3) (dtbpy = di-tert-butylbipyridine) with NFTPT (N-fluoro-1,3,5-trimethylpyridium triflate) afforded the isolable PdIV intermediate (dtbpy)PdIV(Aryl)(CF3)(F)(OTf). Thermolysis of this complex at 80 °C resulted in Aryl–CF3 bond-formation. Detailed experimental and computational mechanistic studies have been conducted to gain insights into the key reductive elimination step. Reductive elimination from this PdIV species proceeds via pre-equilibrium dissociation of TfO− followed by Aryl–CF3 coupling. DFT calculations reveal that the transition state for Aryl–CF3 bond formation involves the CF3 acting as an electrophile with the Aryl ligand acting as a nucleophilic coupling partner. These mechanistic considerations along with DFT calculations have facilitated the design of a 2nd generation system utilizing the tmeda (N,N,N’,N’-tetramethylethylenediamine) ligand in place of dtbpy. The tmeda complexes undergo oxidative trifluoromethylation at room temperature.

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Section: Resultsmentioning

confidence: 99%

“…4,13 The vast majority of known Pd II (Aryl)(CF 3 ) complexes are inert to Aryl–CF 3 coupling at temperatures as high as 150 °C. 24,21 …”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Mechanistic and Computational Studies of Oxidatively-Induced Aryl−CF₃ Bond-Formation at Pd: Rational Design of Room Temperature Aryl Trifluoromethylation

et al. 2011

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“…While trifluoroacetic acid is the least expensive and most desirable reagent in this class, it decarboxylates slowly, and has an estimated half-life of 40,000 years at 15 °C in aqueous solution [10]. Trifluoroacetates have found synthetic utility as fluorinating reagents and will be discussed later in this section; however, decarboxylation typically requires stoichiometric Cu and reaction temperatures >150 °C [11–13]. Other halodifluoroacetic acids decarboxylate more rapidly (Fig.…”

Section: ) Fluorination By Decarboxylative Reagentsmentioning

confidence: 99%

“…Upon heating, the complexes released CO 2 and generated NHC–Cu–CF 3 , which reacted with aryl electrophiles [42]. When aryl halide was used as the solvent, the ligated copper complex provided trifluoromethylated products in higher yields than “ligandless” CuI.…”

Section: ) Fluorination By Decarboxylative Reagentsmentioning

confidence: 99%

Decarboxylative Fluorination Strategies for Accessing Medicinally- Relevant Products

Qiao¹,

Zhu²,

Ambler³

et al. 2014

CTMC

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Fluorinated organic compounds have a long history in medicinal chemistry, and synthetic methods to access target fluorinated compounds are undergoing a revolution. One powerful strategy for the installation of fluorine-containing functional groups includes decarboxylative reactions. Benefits of decarboxylative approaches potentially include: 1) readily available substrates or reagents 2) mild reaction conditions; 3) simplified purification. This focus review highlights the applications of decarboxylation strategies for fluorination reactions to access compounds with biomedical potential. The manuscript highlights on two general strategies, fluorination by decarboxylative reagents and by decarboxylation of substrates. Where relevant, examples of medicinally useful compounds that can be accessed using these strategies are highlighted.

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Emerging Areas in Copper‐Mediated Trifluoromethylations OF ARYL DERIVATIVES: Catalytic and Oxidative Cross‐Coupling Processes

Jouvin¹,

Guissart²,

Theunissen³

et al. 2013

Copper‐Mediated Cross‐Coupling Reactions

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Decarboxylative trifluoromethylation of aryl halides using well-defined copper–trifluoroacetate and –chlorodifluoroacetate precursors

Cited by 93 publications

References 37 publications

Mechanistic and Computational Studies of Oxidatively-Induced Aryl−CF₃ Bond-Formation at Pd: Rational Design of Room Temperature Aryl Trifluoromethylation

Mechanistic and Computational Studies of Oxidatively-Induced Aryl−CF₃ Bond-Formation at Pd: Rational Design of Room Temperature Aryl Trifluoromethylation

Decarboxylative Fluorination Strategies for Accessing Medicinally- Relevant Products

Emerging Areas in Copper‐Mediated Trifluoromethylations OF ARYL DERIVATIVES: Catalytic and Oxidative Cross‐Coupling Processes

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Decarboxylative trifluoromethylation of aryl halides using well-defined copper–trifluoroacetate and –chlorodifluoroacetate precursors

Cited by 93 publications

References 37 publications

Mechanistic and Computational Studies of Oxidatively-Induced Aryl−CF3 Bond-Formation at Pd: Rational Design of Room Temperature Aryl Trifluoromethylation

Mechanistic and Computational Studies of Oxidatively-Induced Aryl−CF3 Bond-Formation at Pd: Rational Design of Room Temperature Aryl Trifluoromethylation

Decarboxylative Fluorination Strategies for Accessing Medicinally- Relevant Products

Emerging Areas in Copper‐Mediated Trifluoromethylations OF ARYL DERIVATIVES: Catalytic and Oxidative Cross‐Coupling Processes

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Mechanistic and Computational Studies of Oxidatively-Induced Aryl−CF₃ Bond-Formation at Pd: Rational Design of Room Temperature Aryl Trifluoromethylation

Mechanistic and Computational Studies of Oxidatively-Induced Aryl−CF₃ Bond-Formation at Pd: Rational Design of Room Temperature Aryl Trifluoromethylation