Copper-Catalyzed Decarboxylative Atom Transfer Radical Addition of Iododifluoroacetate to Alkynyl Carboxylic Acids

Li, Gang; Cao, Yi-Xuan; Luo, Chenguang; Su, Yiming; Li, Yan; Lan, Quan; Wang, Xisheng

doi:10.1021/acs.orglett.6b02216

Cited by 70 publications

(17 citation statements)

References 89 publications

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“…With the aim of evidencing the plausible formation of molecular copper species, we carried out IR and UV‐vis studies starting with both copper(0) nanoparticles and phenylethynylcopper(I) (Figure ) . In the IR region corresponding to the C≡C bond stretching ( ca .…”

Section: Resultsmentioning

confidence: 99%

Making Copper(0) Nanoparticles in Glycerol: A Straightforward Synthesis for a Multipurpose Catalyst

et al. 2017

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Dedicatedt ot he Laboratoire HØtØrochimieF ondamentale et AppliquØeo nt he occasiono fi ts 50 th anniversary.Supporting information for this article is availableunder https://doi.org/10.1002/adsc.201700535.Abstract: Small zero-valent copper nanoparticles (CuNPs) have been straightforwardly preparedf rom Cu(I) andC u(II) precursors in glycerol andi nt he presence of polyvinylpyrrolidone as stabilizer. Thanks to the negligible vaporp ressure of the solvent, these original nano-systems could be directly characterized in glycerol as well as in the solids tate, exhibiting relevantly homogeneous colloidal dispersions,a lso evena fter catalysis. CuNPs coming from the well-defined coordinationc omplex di-m-hydroxobis[(N,N,N',N'-tetramethylethylenediamine)copper(II)] chloride {[Cu(k 2 -N,N-TMEDA)(m-OH)] 2 Cl 2 } have been highly efficient in C-C andC -heteroatom bond formation processes. This newc atalytic system has proved its performance in C-Nc ouplings and in the synthesis of differently substitutedp ropargylic amines throughc ross-dehydrogenative couplings, multi-component reactions such as A 3 (aldehydealkyne-amine) and KA 2 (ketone-alkyne-amine) couplings,a sw ell as in the formationo fh eterocycles such as benzofurans,i ndolizines,a nd quinolines under smoothc onditions.N os ignificant copper amount was detected in the extracted organic compounds from the catalytic phase by inductively coupled plasma-atomic emission spectroscopic (ICP-AES)analyses,p roving ah ighly efficient immobilization of copper nanoparticles in glycerol. From am echanisticp oint of view,s pectroscopic data (infrareda nd ultraviolet-visible spectra) agreew ith asurface-like catalytic reactivity.

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Section: Resultsmentioning

confidence: 99%

Making Copper(0) Nanoparticles in Glycerol: A Straightforward Synthesis for a Multipurpose Catalyst

et al. 2017

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“…Compound III upon protodemetallation furnishes the desired vinyl iodide (Scheme 31). [48] Very recently, Lv and co-workers reported Cucatalyzed difunctionalization of olefins with α-haloacetonitriles constructing an efficient route for the synthesis of γ-halonitriles. This atom transfer radical addition (ATRA) process was found to be providing best yields when 10 mol% CuI along with 20 mol% ligand was employed.…”

Section: Cu-catalyzed 12-difunctionalizationmentioning

confidence: 99%

Transition‐Metal‐Catalyzed Carbohalogenative 1,2‐Difunctionalization of C−C Multiple Bonds

2020

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Transition-metal-catalyzed 1,2-carbohalofunctionalization reactions of CÀ C multiple bonds have emerged rapidly over the past decade as a powerful tool for generating a new carbon-carbon and carbon-halogen bond via transposition of an existing carbon-halogen σ bond. Exploring this highly efficient mode of carbon-carbon multiple bond difunctionalization, various research groups have established novel strategies for the synthesis of organohalides by utilizing wide variety of transition metal catalysts under mild reaction conditions, avoiding stoichiometric waste of by-products, and with improved levels of chemo-, regio-, and stereoselectivities. Most of the 1,2-carbohalo-functionalization reactions involve either the carbon-halogen reductive elimination mechanism or the atom transfer radical addition (ATRA) mechanism. This review summarizes the recent progress in the area of transitionmetal-catalyzed intra-and intermolecular 1,2-carbo-halo-functionalization reactions of carbon-carbon multiple bonds and explicates the underlying potentiality and challenges within the field.

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“…Difluoromethylation can also be accomplished through difluoromethyl reagents of the type Z‐CF 2 ‐Y (where Z,Y≠H, F), such as R 3 SiCF 2 COOEt, BrCF 2 COOEt, FSO 2 CF 2 COOH, TMSCF 2 SO 2 Ph, BrCF 2 SO 2 Ph, BrCF 2 P(O)OEt 2 , or ICF 2 SO 2 Ph . These reagents (Z−CF 2 Y, in which Z,Y≠H, F) append to organic molecules as CF 2 Y groups, and can ultimately be reduced to a CF 2 H motif .…”

Section: Introductionmentioning

confidence: 99%

Difluoromethylation Reactions of Organic Compounds

Yerien

Barata‐Vallejo

Postigo

2017

Chemistry A European J

405

153

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The relevance of the -CF H moiety has attracted considerable attention from organic synthetic and medicinal chemistry communities, because this group can act as a more lipophilic isostere of the carbinol, thiol, hydroxamic acid, or amide groups. Being weakly acidic, the CF H moiety can establish hydrogen-bonding interactions to improve the binding selectivity of biologically active compounds. Therefore, the hydroxyl, amino, and thio substituents of lead structures are routinely replaced by a CF H motif in drug discovery, with great benefits in the pharmacological activity of drugs and drug candidates and agrochemicals. Consequently, the late-stage introduction of CF H is a sought-after strategy in designing bioactive compounds. Secondly, but nonetheless relevant and meaningful, is the study of synthetic pathways to introduce a CF -Y moiety (Y≠H, F) into organic substrates because compounds that contain a CF -Y functionality have also found vast applications in medicinal chemistry and in other areas, such as that of fungicides, insecticides, etc., and thus, this functionality deserves special attention. Although emphasis is made on difluoromethylation strategies to functionalize different families of organic compounds, three main methodological protocols will be presented in this review article for the late-stage introduction of a CF H or CF Y moieties into organic substrates: i) a metal-photoredox catalysis; ii) through transition metal-catalyzed thermal protocols; and iii) from transition-metal-free strategies.

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Copper-Catalyzed Decarboxylative Atom Transfer Radical Addition of Iododifluoroacetate to Alkynyl Carboxylic Acids

Cited by 70 publications

References 89 publications

Making Copper(0) Nanoparticles in Glycerol: A Straightforward Synthesis for a Multipurpose Catalyst

Making Copper(0) Nanoparticles in Glycerol: A Straightforward Synthesis for a Multipurpose Catalyst

Transition‐Metal‐Catalyzed Carbohalogenative 1,2‐Difunctionalization of C−C Multiple Bonds

Difluoromethylation Reactions of Organic Compounds

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