Zn-Mediated Reduction of Oxalyl Chloride Forming CO and Its Application in Carbonylation Reactions

Markovič, Martin; Lopatka, Pavol; Koóš, Peter; Gracza, Tibor

doi:10.1021/acs.orglett.5b02840

Cited by 71 publications

(27 citation statements)

References 51 publications

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“…Considering that TMSCF 3 is a volatile liquid, the evolution of TFE and the subsequent reaction should be conducted separately. Therefore, we designed a simple reaction system consisting of two pressure tubes (TFE generation chamber A and reaction chamber B), which were connected through a three‐way valve (Table ; see the Supporting Information) . TFE was first prepared and stored in chamber A, and was then introduced into chamber B for further reaction.…”

Section: Methodsmentioning

confidence: 99%

TMSCF₃ as a Convenient Source of CF₂=CF₂ for Pentafluoroethylation, (Aryloxy)tetrafluoroethylation, and Tetrafluoroethylation

Xie

et al. 2017

Angewandte Chemie

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An ew method for the on-site preparation of tetrafluoroethylene (TFE) and ap rocedure for its efficient use in pentafluoroethylation by fluoride addition were developed by using as imple two-chamber system. The on-site preparation of TFE was accomplished by dimerization of difluorocarbene derived from (trifluoromethyl)trimethylsilane (TMSCF 3 )u nder mild conditions.O ther fluoroalkylation reactions,s uch as (aryloxy)tetrafluoroethylation and tetrafluoroethylation processes,w ere also achieved using as imilar approach.T his work not only demonstrates ac onvenient and safe approach for the generation and use of TFE in academic laboratories,but also provides anew strategy for pentafluoroethylation.Organofluorine compounds are widely used as functional materials,a grochemicals,a nd pharmaceuticals owing to the unique physical, chemical, and biological features that result from fluorine substitution. [1] Therefore,d eveloping novel methods for the straightforward incorporation of per-o r polyfluorinated groups into organic molecules has received significant attention in both academia and industry. [2] Te trafluoroethylene (TFE, CF 2 =CF 2 ), as abulk fluorochemical for the industrial manufacture of poly(tetrafluoroethylene) and copolymers with other alkenes, [3] is an ideal C2 building block for incorporating fluorinated moieties such as -CF 2 CF 2 -, HCF 2 CF 2 -, and CF 2 = CF-into small molecules. [4] However, TFE is suspected to be carcinogenic, unstable towards radicals,a nd prone to explode when in contact with air,a ll of which in turn require that TFE gas is handled with extreme caution, including during storage and transport. [3d, 5] To overcome the inherent limitations associated with using TFE gas in academic laboratories,s everal TFE precursors have been developed that release TFE gas on site in small amounts.A vailable methods include the reduction of 1,2-dihalotetrafluoroethanes (XCF 2 CF 2 Y; X, Y = Br,Cl) with zinc powder [6] and the pyrolysis of sodium perfluoropropionate [3d] or poly(tetrafluoroethylene) [7] at high temperatures. However,t he restricted availability of XCF 2 CF 2 Ya nd the harsh conditions required for the pyrolysis reactions have limited the utilizations of these methods,thus preventing the development of fluoroalkylation reactions with TFE in common research laboratories.T herefore,t he development of practical and operationally simple methods for the laboratory preparation of TFE is highly desirable.TheRuppert-Prakash reagent (TMSCF 3 )isreadily available and is the most extensively used trifluoromethylation reagent for avariety of applications. [8] In 2011, our group and the Prakash group cooperatively developed an efficient method for the preparation of gem-difluorocyclopropa(e)nes by using TMSCF 3 as an ovel difluorocarbene source in the presence of NaI (Scheme 1a). [9] During the investigation, we noticed that TFE was normally formed as aside product (see the Supporting Information). [9a] In 2014, Baker and coworkers observed that am ixture of TMSCF 3 and NaI in THF cou...

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Section: Methodsmentioning

confidence: 99%

TMSCF₃ as a Convenient Source of CF₂=CF₂ for Pentafluoroethylation, (Aryloxy)tetrafluoroethylation, and Tetrafluoroethylation

Xie

et al. 2017

Angewandte Chemie

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“…By applying the developed protocol, we synthesized a number of amido esters and amido phosphonates. [31][32][33] Although there are difficulties in the handling of CO, few alternate methods have been developed for the carbonylation of alkyl or aryl halides by using nongaseous carbon monoxide sources. thermal conditions.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Amido Esters and Amido Phosphonates through Carbonylation of Diazo Compounds Followed by Nucleophilic Addition Reaction

Ramakrishna

Sivasankar

2017

Eur J Org Chem

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We report a method to produce amido esters and amido phosphonates. Octacarbonyldicobalt [Co2(CO)8] was found to be an efficient nongaseous CO source that could be used as a reagent for the carbonylation of diazo esters and diazo phosphonates under mild reaction conditions. A number of diazo esters and diazo phosphonates smoothly underwent the reaction with CO, which was generated from Co2(CO)8, to produce the corresponding ketenes. The subsequent reaction with an amine afforded the expected amido esters and phosphonates. By applying the developed protocol, we synthesized a number of amido esters and amido phosphonates. Characterization of these compounds was achieved by using standard spectroscopic and analytical techniques as well as crystal structure analysis for four of the products.

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“…Palladium‐catalyzed carbonylation reactions are important transformations generating carboxylic acid derivatives. In laboratory scale the use of carbon monoxide gas is inconvenient and several attempts are described to avoid this toxic reagent . One alternative found is the use of metal carbonyl compounds such as molybdenum hexacarbonyl .…”

Section: Resultsmentioning

confidence: 99%

Heck Reactions and Carbonylations of Alkenyl Nonaflates – Synthesis of Tetradehydroamino Acids and α,β‐Unsaturated Carboxylic Acids

Taszarek

Reißig

2016

ChemistrySelect

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In a brief exploratory study we investigated Heck reactions of several alkenyl nonaflates with a protected dehydroalanine derivative. Whereas simple alkenyl nonaflates provided the expected 1,3-dienes in good to excellent yields, more complex oxa-bridged bicyclic substrates gave poorer results. Nevertheless, this approach is of interest for the synthesis of tetradehydroamino acids. Palladium-catalyzed carbonylations of alkenyl nonaflates employing molybdenum hexacarbonyl as convenient carbon monoxide source leading to esters or to carboxylic acids were also studied. Microwave conditions seem to be superior to purely thermal conditions. With an oxygenbridged bicyclic alkenyl nonaflate the expected carboxylic acid was isolated, however, the formation of a tropone derivative as a result of an acid-promoted fragmentation was also observed.

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Zn-Mediated Reduction of Oxalyl Chloride Forming CO and Its Application in Carbonylation Reactions

Cited by 71 publications

References 51 publications

TMSCF₃ as a Convenient Source of CF₂=CF₂ for Pentafluoroethylation, (Aryloxy)tetrafluoroethylation, and Tetrafluoroethylation

TMSCF₃ as a Convenient Source of CF₂=CF₂ for Pentafluoroethylation, (Aryloxy)tetrafluoroethylation, and Tetrafluoroethylation

Synthesis of Amido Esters and Amido Phosphonates through Carbonylation of Diazo Compounds Followed by Nucleophilic Addition Reaction

Heck Reactions and Carbonylations of Alkenyl Nonaflates – Synthesis of Tetradehydroamino Acids and α,β‐Unsaturated Carboxylic Acids

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Zn-Mediated Reduction of Oxalyl Chloride Forming CO and Its Application in Carbonylation Reactions

Cited by 71 publications

References 51 publications

TMSCF3 as a Convenient Source of CF2=CF2 for Pentafluoroethylation, (Aryloxy)tetrafluoroethylation, and Tetrafluoroethylation

TMSCF3 as a Convenient Source of CF2=CF2 for Pentafluoroethylation, (Aryloxy)tetrafluoroethylation, and Tetrafluoroethylation

Synthesis of Amido Esters and Amido Phosphonates through Carbonylation of Diazo Compounds Followed by Nucleophilic Addition Reaction

Heck Reactions and Carbonylations of Alkenyl Nonaflates – Synthesis of Tetradehydroamino Acids and α,β‐Unsaturated Carboxylic Acids

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TMSCF₃ as a Convenient Source of CF₂=CF₂ for Pentafluoroethylation, (Aryloxy)tetrafluoroethylation, and Tetrafluoroethylation

TMSCF₃ as a Convenient Source of CF₂=CF₂ for Pentafluoroethylation, (Aryloxy)tetrafluoroethylation, and Tetrafluoroethylation