Palladium-Catalyzed C–H Trifluoroethoxylation of <i>N</i>-Sulfonylbenzamides

Yang, Long; Li, Shangda; Cai, Lei; Ding, Yongzheng; Fu, Lei; Cai, Zhihua; Ji, Huafang; Li, Gang

doi:10.1021/acs.orglett.7b01103

Cited by 51 publications

(36 citation statements)

References 104 publications

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“…Also, reactions using some of the difluorocarbene sources require either special reaction apparatus, elevated temperatures, or strong bases. To alleviate some of these limitations and establish milder reaction conditions, visible‐light photoredox catalysis has been used for the generation of the difluorocarbene intermediate . More recently, Ngai et al.…”

Section: Synthesis Of Difluoromethoxylated Compoundsmentioning

confidence: 99%

“…In 2017, Fu and co‐workers reported a strategy that enabled preparation of aromatic difluoromethyl ethers under visible‐light photocatalytic conditions (Scheme ) . The difluorocarbene species, :CF 2 , was generated in situ from commercially available and easy‐to‐handle difluorobromoacetic acid (BrCF 2 CO 2 H) in the presence of fac ‐Ir(ppy) 3 at room temperature upon irradiation with visible light.…”

Section: Synthesis Of Difluoromethoxylated Compoundsmentioning

confidence: 99%

“…On the basis of these results, Fu and co‐workers postulated that the reaction begins with photoexcitation of fac ‐Ir(ppy) 3 (Scheme b). The cesium carboxylate 12.2 ( E p =−1.29 V vs. SCE) is then reduced by the photoexcited * fac ‐Ir(ppy) 3 ( E 1/2 IV/*III =−1.73 V vs. SCE) to afford the α‐carbonyl radical 12.3 . Subsequently, a SET oxidation of 12.3 by fac ‐Ir(ppy) 3 + regenerates the ground‐state fac ‐Ir(ppy) 3 and liberates the difluorocarbene intermediate 12.4 , which is trapped by the phenoxide 12.5 and then protonated to afford the desired aryl difluoromethyl ether 12.6 .…”

Section: Synthesis Of Difluoromethoxylated Compoundsmentioning

confidence: 99%

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Synthesis of Tri‐ and Difluoromethoxylated Compounds by Visible‐Light Photoredox Catalysis

2019

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Trifluoromethoxy (OCF3) and difluoromethoxy (OCF2H) groups are fluorinated structural motifs that exhibit unique physicochemical characteristics. Incorporation of these substituents into organic molecules is a highly desirable approach used in medicinal chemistry and drug discovery processes to alter the properties of a parent compound. Recently, tri‐ and difluoromethyl ethers have received increasing attention and several innovative strategies to access these valuable functional groups have been developed. The focus of this Minireview is the use of visible‐light photoredox catalysis in the synthesis of tri‐ and difluoromethyl ethers. Recent photocatalytic strategies for the formation of O−CF3, C−OCF3, O−CF2H, and C−OCF2H bonds as well as other transformations leading to the construction of ORF groups are discussed herein.

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Section: Synthesis Of Difluoromethoxylated Compoundsmentioning

confidence: 99%

Section: Synthesis Of Difluoromethoxylated Compoundsmentioning

confidence: 99%

Section: Synthesis Of Difluoromethoxylated Compoundsmentioning

confidence: 99%

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Synthesis of Tri‐ and Difluoromethoxylated Compounds by Visible‐Light Photoredox Catalysis

2019

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“…Under a similar context, the secondary amine‐catalyzed [2+2+2] annulation reaction of nitroolefins 2 , aldehydes 1 , and N ‐protected‐isatin ketamines 102 to the synthesis of spiro‐oxindole piperidine derivatives via an organocatalytic Michael‐aza‐Henry‐hemiaminalization cascade reaction was disclosed by our group in 2017 (Scheme ) . The reaction parameters were systematically screened, and conducting the reaction in MeCN at 40 °C with DBU as base was found to yield excellent results.…”

Section: Asymmetric Catalysis With Chiral Aminementioning

confidence: 99%

Organocatalytic Asymmetric Cascade Reactions Based on Gamma‐Nitro Carbonyl Compound

Guo

Peng

et al. 2018

The Chemical Record

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The significant advancements in asymmetric organocascade reactions have been accomplished during the past decades, paving the way to the efficient and stereoselective construction of structurally complex scaffolds from simple and readily available starting materials. Nitro-containing cyclic compounds have become a privileged molecular library given their broad and promising activities in various therapeutic areas. In various approaches to build these valuable scaffolds, the utility of γ-nitrocarbonyl intermediates is one of the most efficient approaches due to its high efficiency, reliability and versatility. The strategies and catalyst systems described here highlight recent advances in the enantioselective synthesis of nitro-containing cyclic molecules via organocascade strategies based on γ-nitrocarbonyl intermediates. Various organocatalysts with distinct activation modes have found application in providing these sophisticated compounds. This review is organized according to the types of organocatalyst. These methods are of importance for the construction of complex chiral cyclic frameworks and the design of new pharmaceutical compounds. We believe that compounds based on nitro-containing cyclic skeletons have the potential to provide novel therapeutic agents and useful biological tools.

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“…The commercially available bromodifluoroacetic acid (BrCF 2 CO 2 H, CAS number: 354‐08‐5) was employed in the difluoromethylation of phenols and thiophenols ( 222 ) under visible light with a 23 W CFL . Screening of photocatalysts, bases, and solvents showed that the combination of fac ‐Ir(III)(ppy) 3 , Cs 2 CO 3 , and DMF, respectively, was appropriate for the efficiency of difluoromethylation process (Scheme ).…”

Section: General Introductionmentioning

confidence: 99%

Progress in Difluoroalkylation of Organic Substrates by Visible Light Photoredox Catalysis

2019

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Thes electivei ncorporation of fluorinated motifs, in particularC F 2 FG (FG = af unctional group) and CF 2 Hg roups,i ntoo rganic compounds has attrracted increasing attention since organofluorine molecules are of the utmost importance in the areas of nuclear imaging,pharmaceutical, agrochemical, and material sciences.Avariety of synthetic approachesh as been employed in late-stage difluoroalkylationr eactions.V isible light photoredox catalysis for the production of CF 2 FG and CF 2 Hr adicalsh as providedamore sustainable alternative to other conventional radical-triggered reactions from the viewpoint of safety,c ost, availability,a nd "green"c hemistry.Awide range of difluoroalkylating reagents has been successfully implemented in these organic transformationsi nt he presence of transitionm etal complexes or organic photocatalysts.I nmost cases, upon excitation via visible light irradiation with fluorescent light bulbs or blue light-emitting diode (LED) lamps,t hese photocatalysts can act as both reductivea nd oxidative quenchers,t hus enabling the applicationo fe lectron-donoro re lectron-acceptor difluoroalkylating reagents for the generation of CF 2 FG andC F 2 Hr adicals.S ubsequent radical addition to substrates and additional organic transformations affordt he corresponding difluoroalkylatedd erivatives.T he presentr eview describes the distinct strategies for the transitionm etal-and organic-pho-tocatalyzed difluoroalkylation of ab road range of organic substrates by visible light irradiationr eported in the literature since 2014.

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Palladium-Catalyzed C–H Trifluoroethoxylation of N-Sulfonylbenzamides

Cited by 51 publications

References 104 publications

Synthesis of Tri‐ and Difluoromethoxylated Compounds by Visible‐Light Photoredox Catalysis

Synthesis of Tri‐ and Difluoromethoxylated Compounds by Visible‐Light Photoredox Catalysis

Organocatalytic Asymmetric Cascade Reactions Based on Gamma‐Nitro Carbonyl Compound

Progress in Difluoroalkylation of Organic Substrates by Visible Light Photoredox Catalysis

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