Fluorodecarboxylation: Synthesis of aryl trifluoromethyl ethers (ArOCF3) and thioethers (ArSCF3)

Krishanmoorthy, Sankarganesh; Schnell, Simon; Dang, Huong; Fu, Feng; Prakash, G. K. Surya

doi:10.1016/j.jfluchem.2017.07.017

Cited by 33 publications

(19 citation statements)

References 25 publications

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“…The reaction performs well with moderately electron‐rich and electron‐poor substrates but fails for substrates with strong electron‐donating substituents (e. g. methoxy) probably due to competing electrophilic fluorination on the aromatic ring. A similar method was introduced by Prakash and co‐workers [214] . Their protocol employs Selectfluor as a fluorine source in the presence of trifluoroacetic acid.…”

Section: Decarboxylative C‐halogen Bond Formationmentioning

confidence: 99%

Decarboxylation‐Initiated Intermolecular Carbon‐Heteroatom Bond Formation

Zeng¹,

Feceu

Sivendran

et al. 2021

Adv Synth Catal

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Carboxylic acids are among the most used feedstock chemicals due to their great structural diversity and easy handling. The use of carboxylic acids and their derivatives in decarboxylative couplings has proven to be a valuable tool for the construction of C−C and C‐heteroatom bonds. This synthetic strategy provides a complementary bond disconnection to traditional cross‐coupling methods. In this review, we provide a comprehensive overview of decarboxylation‐initiated intermolecular C‐heteroatom bond formation, outlining several main mechanistic concepts combined with early examples and highlighting the achievements made in the past decade until January 2021. In these reactions, carboxylic acids and their derivatives undergo initial decarboxylation and then react with other heteroatom electrophiles and nucleophiles, thus replacing the carboxylate group with a valuable and prevalent heteroatom functionality.

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Section: Decarboxylative C‐halogen Bond Formationmentioning

confidence: 99%

Decarboxylation‐Initiated Intermolecular Carbon‐Heteroatom Bond Formation

Zeng¹,

Feceu

Sivendran

et al. 2021

Adv Synth Catal

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“…To elucidate this divergent mechanism, we performed several control experiments. When a preformed nucleophilic substitution product 7 was subjected to the reaction condition, no decarboxylative protonation took place ,. When the reaction was arrested after two hours, a mixture of starting material and product was obtained.…”

Section: Resultsmentioning

confidence: 99%

Triple Mode of Alkylation with Ethyl Bromodifluoroacetate: N, or O‐Difluoromethylation, N‐Ethylation and S‐(ethoxycarbonyl)difluoromethylation

et al. 2018

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In this report, we have explored a triple mode of chemical reactivity of ethyl bromodifluoroacetate. Typically, bromodifluoroacetic acid has been used as a difluorocarbene precursor for difluoromethylation of soft nucleophiles. Here we have disclosed nucleophilicity and base dependent divergent chemical reactivity of ethyl bromodifluoroacetate. It furnishes lithium hydroxide and cesium carbonate promoted difluoromethylation of tosyl-protected aniline and electron-deficient phenols respectively. Interestingly, switching the base from lithium hydroxide to 4-N,N-dimethylamino pyridine (DMAP) tosyl-protected anilines afforded the corresponding N-ethylation product. Whereas, highly nucleophilic thiophenols furnished the corresponding Scarboethoxydifluoromethylation product via a rapid S N 2 attack to the bromine atom prior to the ester hydrolysis. This mechanistic divergence was established through several control experiments. It was revealed that difluoromethylation reaction proceeds through a tandem in situ ester hydrolysis/decarboxylativedebrominative difluorocarbene formation and subsequent trapping by the soft nucleophile-NHTs or electrondeficient phenolic ÀOH groups. In the presence of DMAP the hydrolysis of the ester is perturbed instead a nucleophilic attack at the ethyl moiety provides the N-ethylation product. Hence, besides the development of a practical base-promoted N-difluoromethylation of amines and electron-deficient phenols, divergent reactivity pattern of inexpensive and user-friendly ethyl bromodifluoroacetate has been explored.

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“…Later, Prakash presented a similar approach to create the same type of substrates, utilizing Selectfluor as a fluorine source and a different strong acid. 392 The yields of this modification are generally lower.…”

Section: The Fluorodecarboxylation Reactionmentioning

confidence: 99%

Decarboxylative Halogenation of Organic Compounds

2020

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Decarboxylative halogenation, or halodecarboxylation, represents one of the fundamental key methods for the synthesis of ubiquitous organic halides. The method is based on conversion of carboxylic acids to the corresponding organic halides via selective cleavage of a carbon–carbon bond between the skeleton of the molecule and the carboxylic group and the liberation of carbon dioxide. In this review, we discuss and analyze major approaches for the conversion of alkanoic, alkenoic, acetylenic, and (hetero)aromatic acids to the corresponding alkyl, alkenyl, alkynyl, and (hetero)aryl halides. These methods include the preparation of families of valuable organic iodides, bromides, chlorides, and fluorides. The historic and modern methods for halodecarboxylation reactions are broadly discussed, including analysis of their advantages and drawbacks. We critically address the features, reaction selectivity, substrate scopes, and limitations of the approaches. In the available cases, mechanistic details of the reactions are presented, and the generality and uniqueness of the different mechanistic pathways are highlighted. The challenges, opportunities, and future directions in the field of decarboxylative halogenation are provided.

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Fluorodecarboxylation: Synthesis of aryl trifluoromethyl ethers (ArOCF3) and thioethers (ArSCF3)

Cited by 33 publications

References 25 publications

Decarboxylation‐Initiated Intermolecular Carbon‐Heteroatom Bond Formation

Decarboxylation‐Initiated Intermolecular Carbon‐Heteroatom Bond Formation

Triple Mode of Alkylation with Ethyl Bromodifluoroacetate: N, or O‐Difluoromethylation, N‐Ethylation and S‐(ethoxycarbonyl)difluoromethylation

Decarboxylative Halogenation of Organic Compounds

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