Solid supported fluoronitroaryl triazenes as immobilized and convertible Sanger reagents – synthesis and SNAr reactions towards a novel preparation of 1-alkyl-5-nitro-1H-benzotriazolesElectronic supplementary information (ESI) available: experimental procedures. See http://www.rsc.org/suppdata/cc/b2/b201489k/

Lormann, Matthias; Walker, Catherine H.; Es‐Sayed, Mazen; Bräse, Stefan

doi:10.1039/b201489k

Cited by 25 publications

(11 citation statements)

References 23 publications

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“…25 Starting from resin 3{6} or 3{7}, reaction of the model phenol 4{6} yielded the diaryl ether resins 5{6,6} and 5{7,6}, respectively. The use of potassium carbonate proved to be most efficient for complete conversion (Scheme 4).…”

Section: Resultsmentioning

confidence: 99%

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Efficient Synthesis of Highly Substituted Diaryl Ethers on Solid Supports Using the Ullmann Reaction

2004

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Diaryl ethers are important structures found in both nature and biologically active compounds. Some diaryl ethers exert considerable pharmacological activity, such as perrottetines, riccardin B, and marchantin quinone, all of which influence blood coagulation; 1 the antiviral cyclic peptide K-13; 2 and the glycopeptide antibiotics Vancomycin, Teicoplanin, and Complestatin. 2-5 Until recently, the synthesis of diaryl ethers having sensitive groups remained a challenge. 6-8 Therefore, diaryl ethers are a promising class of potentially useful pharmacologically active compounds, and their synthesis in liquid phase, particularly by nucleophilic aromatic substitution and Ullmann-type reactions, has found widespread application in organic chemistry. 9 The solid-phase synthesis of diaryl ethers mainly focuses on nucleophilic displacement of fluoronitroarenes in an intermolecular or intramolecular sense, furnishing 7-, 10 13-, 11 14-, 11-13 15-, 16-, 11,12,14 and 17-membered rings, 11 as demonstrated in the total synthesis of OF 4949. 14 Analogously, cyclic alkylaryl ethers 15 and thioethers 16 were synthesized using this strategy. Results and DiscussionWe were intrigued by the possibility of generating diaryl ethers on solid supports using the Ullmann reaction variant reported by Nicolaou et al., 5 since this reaction is particularly suitable for the synthesis of triazenyl-substituted diaryl ether and has been used in the total synthesis of the glycopeptide antibiotic Vancomycin. 5,17 The reaction temperature required is in contrast to classical Ullmann conditions compatible with solid-phase chemistry. Triazenes are masked diazonium ions and are convertible to a broad range of heterocycles. 18 In this manuscript, we disclose the first solid-phase UllmannNicolaou reaction.The required ortho-halo triazene resins 1{1-6} were synthesized via optimized procedures from anilines and arylmethylaminomethyl polystyrenes, which are available from chloromethylated polystyrene (1-2% cross-linked) in one synthetic step in large quantities (Scheme 1). 19,20 Five different anilines 21 were immobilized on benzylaminesubstituted Merrifield resin under standard conditions using this route. 22 The loadings were determined by elemental analysis.The Nicolaou variant of the Ullmann reaction was performed on the resins 3{1-4} (500-mg scale) at 75-85°C in acetonitrile/pyridine or dimethylformamide/pyridine for 36-48 h with 1.1-5.0 equiv of eight different phenols 4{1-8} 21 in the presence of the soluble copper complex CuBr‚SMe 2 (1 equiv) (Scheme 2). During the reaction, a color change of the resin from a slightly reddish color into a deep red color was observed. Heteroatoms such as nitrogen or oxygen atoms and simple functional groups (double bonds, amides, amines) at the phenolic moiety were tolerated; however, it was puzzling to note that extension to mono and

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Section: Resultsmentioning

confidence: 99%

“…25 The novel azides 6 (∼17 to 80 mg) were obtained in purities >90% and yields between 34 and 95% without further purification, as judged by integration of the GC or 1 H NMR signals.…”

Section: Resultsmentioning

confidence: 99%

Efficient Synthesis of Highly Substituted Diaryl Ethers on Solid Supports Using the Ullmann Reaction

2004

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“…Generally, nucleophilic aromatic substitutions on diazonium salts are yet rare in literature with few synthetic applications, [4] whereas drawbacks arise from the necessity to use the nucleophile as solvent (Scheme 1 B) [4a] or the requirement to protect the diazonium unit as a triazene (Scheme 1 C). [4b] On the other hand, the presence of a diazonium group on an aryl‐alkyl ether such as 4 would enable a broad range of further functionalizations, [5, 6] which cannot be achieved with the traditional dinitro substitution pattern.…”

Section: Methodsmentioning

confidence: 99%

“…Donor‐substituted anilines (e.g., N , N ‐diethyl‐1,4‐phenylenediamine) again act as reductants and partners for azo coupling to yield complex mixtures. Interestingly, acceptor‐substituted anilines provided benzotriazoles via substitution of the fluorine atom and cyclization involving the diazonium unit (see Scheme 1 C and the Supporting Information) [4b] …”

Section: Methodsmentioning

confidence: 99%

2‐Fluoro‐5‐nitrophenyldiazonium: A Novel Sanger‐Type Reagent for the Versatile Functionalization of Alcohols

Fischer

Heinrich

2021

Chemistry A European J

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“…310 Reports on fluoride displacement in aryl fluorides with amines in the absence of a palladium catalyst are found in the literature, but in these cases the aromatic ring was activated with electron-withdrawing nitro groups in the ortho-or para-positions. [311][312][313] Iron-catalyzed arylation of Merrifield resin-bound piperazine was also achieved (11-72% yields). 314 Wang and Huang adapted a palladium-catalyzed threecomponent coupling of aryl halides, dienes, and amines to SPS on Rink resin (~35-81% yields).…”

Section: Scheme 35mentioning

confidence: 97%

N-Alkylation Reactions and Indirect Formation of Amino Functionalities in Solid-Phase Synthesis

Olsen¹,

Franzyk²,

Jaroszewski³

2005

Synthesis

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Aliphatic and aromatic amino functionalities are present in a wide variety of natural products and drugs, as well as in synthetic small molecular probes with therapeutic and/or diagnostic potential in drug discovery. As solid-phase synthesis and combinatorial chemistry have emerged as important tools for generation of compound libraries, development of broad-scope and efficient chemistry for the introduction of various functional groups into resinanchored substrates is highly important. Herein, we present a review of the literature concerning formation of the amino functionality on solid phase.

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Cited by 25 publications

References 23 publications

Efficient Synthesis of Highly Substituted Diaryl Ethers on Solid Supports Using the Ullmann Reaction

Efficient Synthesis of Highly Substituted Diaryl Ethers on Solid Supports Using the Ullmann Reaction

2‐Fluoro‐5‐nitrophenyldiazonium: A Novel Sanger‐Type Reagent for the Versatile Functionalization of Alcohols

N-Alkylation Reactions and Indirect Formation of Amino Functionalities in Solid-Phase Synthesis

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