Although fluorinated compounds have found widespread applications in the chemical and materials industries, general site-specific C(sp(3))-F bond formations are still a challenging task. We report here that with catalysis of AgNO(3), various aliphatic carboxylic acids undergo efficient decarboxylative fluorination SELECTFLUOR(®) reagent aqueous solution, leading to synthesis corresponding alkyl fluorides satisfactory yields under mild conditions. This radical method is not only but also...

We report herein a mild and catalytic intramolecular aminofluorination of unactivated alkenes. Thus, with the catalysis AgNO3, reactions various N-arylpent-4-enamides Selectfluor reagent in CH2Cl2/H2O led to efficient synthesis 5-fluoromethyl-substituted γ-lactams. A mechanism involving silver-catalyzed oxidative generation amidyl radicals silver-assisted fluorine atom transfer was proposed.

C(sp(3))-C(sp) bond formations are of immense interest in chemistry and material sciences. We report herein a convenient, radical-mediated catalytic method for cross-coupling. Thus, with AgNO(3) as the catalyst K(2)S(2)O(8) oxidant, various aliphatic carboxylic acids underwent decarboxylative alkynylation commercially available ethynylbenziodoxolones aqueous solution under mild conditions. This site-specific is not only general efficient but also functional group compatible. In addition, it...

Decarboxylative halogenation of carboxylic acids, the Hunsdiecker reaction, is one fundamental functional group transformations in organic chemistry. As initial method requires preparations strictly anhydrous silver carboxylates, several modifications have been developed to simplify procedures. However, these methods suffer from use highly toxic reagents, harsh reaction conditions, or limited scope application. In addition, none catalytic for aliphatic acids. this Article, we report first...

We report herein a mild and catalytic phosphonofluorination of unactivated alkenes. With catalysis by AgNO3, the condensation various alkenes with diethyl phosphite Selectfluor reagent in CH2Cl2/H2O/HOAc at 40 °C led to efficient synthesis β-fluorinated alkylphosphonates good stereoselectivity wide functional group compatibility. A mechanism involving silver-catalyzed oxidative generation phosphonyl radicals silver-assisted fluorine atom transfer is proposed.

We report herein an efficient and general method for the decarboxylative azidation of aliphatic carboxylic acids. Thus, with AgNO3 as catalyst K2S2O8 oxidant, reactions various acids tosyl azide or pyridine-3-sulfonyl in aqueous CH3CN solution afforded corresponding alkyl azides under mild conditions. A broad substrate scope wide functional group compatibility were observed. radical mechanism is proposed this site-specific azidation.

The silver-catalyzed decarboxylative trifluoromethylation of aliphatic carboxylic acids is described. With AgNO3 as the catalyst and K2S2O8 oxidant, reactions with (bpy)Cu(CF3)3 (bpy = 2,2′-bipyridine) ZnMe2 in aqueous acetonitrile at 40 °C afford corresponding products good yield. protocol applicable to various primary secondary alkyl exhibits wide functional group compatibility. Mechanistic studies reveal intermediacy –Cu(CF3)3Me, which undergoes reductive elimination subsequent oxidation...

Reported herein is an unprecedented protocol for trifluoromethylation of unactivated aliphatic C(sp3 )-H bonds. With Cu(OTf)2 as the catalyst, reaction N-fluoro-substituted carboxamides (or sulfonamides) with Zn(CF3 )2 complexes provides corresponding δ-trifluoromethylated in satisfactory yields under mild conditions. A radical mechanism involving 1,5-hydrogen atom transfer N-radicals followed by CF3 -transfer from CuII -CF3 to thus formed alkyl radicals proposed.

We report herein an efficient and general method for the deboronofluorination of alkylboronates. Thus, with catalysis AgNO3, reactions various alkylboronic acids or their pinacol esters Selectfluor reagent in acidic aqueous solution afforded corresponding alkyl fluorides under mild conditions. A broad substrate scope wide functional group compatibility were observed. radical mechanism is proposed this site-specific fluorination.

The copper-mediated trifluoromethylation of alkyl radicals is described. combination Et3SiH and K2S2O8 initiates the radical reactions bromides or iodides with BPyCu(CF3)3 (BPy = 2,2′-bipyridine) in aqueous acetone at room temperature to afford corresponding products good yield. protocol applicable various primary secondary halides exhibits wide functional group compatibility. A mechanism involving trifluoromethyl transfer from Cu(II)–CF3 intermediates proposed.

We report herein an unprecedented protocol for aminotrifluoromethylation of alkenes. With Cu(OTf)2 as the catalyst, reaction alkenes, (bpy)Zn(CF3)2, and N-fluorobis(benzenesulfonyl)imide (NFSI) at room temperature provides corresponding products in satisfactory yields with high regioselectivity opposite to those driven by CF3 radical addition. The method exhibits a broad substrate scope wide functional group compatibility. A mechanism involving N-radical addition alkenes followed...

The copper-assisted radical carbofluorination of unactivated alkenes with fluoride ions is described. With [Cu(L3)F2]H2O (L3 = 4,4'-di(methoxycarbonyl)-2,2'-bipyridine) as the fluorine source and [Ag(DMPhen)(MeCN)]BF4 (DMPhen 2,9-dimethyl-1,10-phenanthroline) chloride scavenger, reaction CCl4 in acetonitrile provided corresponding products satisfactory yields. protocol exhibited a wide functional group compatibility broad substrate scope could be extended to use variety activated alkyl...

Abstract Reported herein is an unprecedented protocol for C(sp 3 )‐phosphinylation. With 1 mol % 4CzIPN (1,2,3,5‐tetrakis(carbazol‐9‐yl)‐4,6‐dicyanobenzene) as the catalyst, visible light induced reaction of redox‐active esters aliphatic carboxylic acids with dimethyl arylphosphonites or diethyl alkylphosphonites at room temperature provides corresponding decarboxylative phosphinylation products in satisfactory yields. The exhibits broad substrate scope and wide functional‐group...

The copper-catalyzed intramolecular coupling of aryl bromides with 1,3-dicarbonyls via a six-membered ring closure was examined. With CuI (10 mol %) as the catalyst, N,N'-dimethylethylenediamine ligand, and Cs2CO3 base, reactions alpha-(2-bromobenzyl)-beta-keto esters in THF at refluxing temperature afforded corresponding substituted 4H-1-benzopyrans high yields O-arylation. On other hand, delta-(2-bromophenyl)-beta-keto dioxane led to formation 3,4-dihydronaphthalen-2(1H)-one derivatives...

We report herein the transition-metal-free azidofluorination of unactivated alkenes. Thus, condensation various alkenes with TMSN3 and Selectfluor in aqueous CH3CN at RT led to efficient regioselective synthesis β-fluorinated alkyl azides excellent functional group compatibility good stereoselectivity. A single electron transfer mechanism involving oxidative generation azidyl radicals is proposed.

Using a combination of ketones and Selectfluor to mimic α-fluoroketones, formal fluorine-atom-transfer radical addition (F-ATRA) reactions were successfully developed in high efficiency.

Direct decarboxylative radical allylation of aliphatic carboxylic acids is described. With K2S2O8 as the oxidant and AgNO3 catalyst, reactions with allyl sulfones in aqueous CH3CN solution gave corresponding alkenes satisfactory yields under mild conditions. This site-specific method applicable to all primary, secondary, tertiary alkyl exhibits wide functional group compatibility.

The trifluoromethylalkynylation of unactivated alkenes with alkynyl sulfones and Togni's reagent was developed. reaction catalyzed by 2,4,6-trimethylpyridine, leading to various β-trifluoromethylated alkynes under metal-free conditions a broad substrate scope wide functional group compatibility. A mechanism involving catalytic nonchain radical processes is proposed.

The silver-catalyzed Hunsdiecker bromination of aliphatic carboxylic acids is described. With Ag(Phen)2OTf as the catalyst and dibromoisocyanuric acid brominating agent, various underwent decarboxylative to provide corresponding alkyl bromides under mild conditions. This method not only efficient general but also enjoys wide functional group compatibility. An oxidative radical mechanism involving Ag(II) intermediates proposed.

Acylphosphonates having the 5,5-dimethyl-1,3,2-dioxophosphinanyl skeleton are developed as efficient intermolecular radical acylation reagents, which enable cobalt-catalyzed Markovnikov hydroacylation of unactivated alkenes at room temperature under mild conditions. The protocol exhibits broad substrate scope and wide functional group compatibility, providing branched ketones in satisfactory yields. A mechanism involving Co–H mediated hydrogen atom transfer subsequent trapping alkyl radicals...