N-fluorobenzenesulfonimide Research Articles

The Unusual Redox Properties of Fluoroferrocenes Revealed through a Comprehensive Study of the Haloferrocenes

We report the synthesis and full characterization of the entire haloferrocene (FcX) and 1,1′-dihaloferrocene (fcX2) series (X = I, Br, Cl, F; Fc = ferrocenyl, fc = ferrocene-1,1′-diyl). Finalization of this simple, yet intriguing set of compounds has been delayed by synthetic challenges associated with the incorporation of fluorine substituents. Successful preparation of fluoroferrocene (FcF) and 1,1′- difluoroferrocene (fcF2) were ultimately achieved using reactions between the appropriate lithiated ferrocene species and N-fluorobenzenesulfonimide (NFSI). The crude reaction products, in addition to those resulting from analogous preparations of chloroferrocene (FcCl) and 1,1′-dichloroferrocene (fcCl2), were utilized as model systems to probe the limits of a previously reported “oxidative purification” methodology. From this investigation and careful solution voltammetry studies, we find that the fluorinated derivatives exhibit the lowest redox potentials of each of the FcX and fcX2 series. This counterintuitive result is discussed with reference to the spectroscopic, structural, and first-principles calculations of these and related materials.

Transition-Metal-Free Fluoroarylation of Diazoacetamides: A Complementary Approach to 3-Fluorooxindoles.

An efficient transition-metal-free fluoroarylation reaction of N-aryl diazoacetamides with NFSI (N-fluorobenzenesulfonimide) is described. This reaction directly provides 3-fluorooxindole derivatives in yields of 67-93% with high selectivity via a carbene-free process under mild reaction conditions.

An unprecedented oxidative intermolecular homo coupling reaction between two sp3C–sp3C centers under metal-free condition

An unprecedented formation of benzylic sp3C–sp3C coupled dibenzylic products has been illustrated. The reactions have been carried out in the presence of three oxidizing reagents, i.e., diacetoxy-iodobenzene (IBDA), N-fluorobenzenesulfonimide (NFSI), and pyridine (Py) using toluene derivatives.

The Organocatalytic α‐Fluorination of Chiral γ‐Nitroaldehydes: the Challenge of Facing the Construction of a Quaternary Fluorinated Stereocenter

Chiral γ‐nitroaldehydes 1 are easily accessible by the organocatalytic Michael addition of aldehydes to nitroalkenes. In this paper, we report the organocatalytic fluorination of 1 with N‐fluorobenzenesulfonimide (NFSI) leading to the highly stereoselective construction of a challenging quaternary fluorinated stereocenter at the α position of α,α‐dialkyl aldehydes. The reaction takes place via a chiral trisubstituted enamine, so far rather unexplored in the field of organocatalysis. Fluorinated products 3 are direct precursors of chiral monofluorinated 3,4‐polysubstituted pyrrolidines. Mechanistic details are discussed with the aid of computational results.

Investigation of Meyer–Schuster Rearrangement Promoted by a Samarium(III) Triflate/N‐Fluorobenzenesulfonimide Lewis Acid System

AbstractThe acceleration effect from the addition of N‐fluorobenzenesulfonimide (NFSI) to a samarium(III) triflate catalyzed Meyer–Schuster rearrangement under microwave irradiation was studied. Reaction rate plots indicate that the Sm(OTf)3/NFSI system is especially suitable for unreactive substrates towards the Meyer–Schuster rearrangement. The mechanism was probed by a crossover experiment using 18O‐labeled substrates.

N-Heterocyclic Carbene Catalyzed andN-Fluorobenzenesulfonimide Mediated Oxidative Synthesis of Perester and Amide

The first study of oxidative synthesis of simple tert-butyl peresters and amides enabled by N-heterocyclic car- bene-catalysis using N-fluorobenzenesulfonimide (NFSI) as oxidant is described. The reaction proceeds with green, high yield, board substrate scope and room temperature.

Copper-catalyzed decarboxylative stereospecific amidation of cinnamic acids with N-fluorobenzenesulfonimide

A copper-catalyzed decarboxylative coupling of cinnamic acids with N-fluorobenzenesulfonimide (NFSI), to give the substituted (E)-amination products stereospecifically, has been realized.

The Unusual Redox Properties of Fluoroferrocenes Revealed through a Comprehensive Study of the Haloferrocenes

We report the synthesis and full characterization of the entire haloferrocene (FcX) and 1,1′-dihaloferrocene (fcX2) series (X = I, Br, Cl, F; Fc = ferrocenyl, fc = ferrocene-1,1′-diyl). Finalization of this simple, yet intriguing set of compounds has been delayed by synthetic challenges associated with the incorporation of fluorine substituents. Successful preparation of fluoroferrocene (FcF) and 1,1′-difluoroferrocene (fcF2) were ultimately achieved using reactions between the appropriate lithiated ferrocene species and N-fluorobenzenesulfonimide (NFSI). The crude reaction products, in addition to those resulting from analogous preparations of chloroferrocene (FcCl) and 1,1′-dichloroferrocene (fcCl2), were utilized as model systems to probe the limits of a previously reported “oxidative purification” methodology. From this investigation and careful solution voltammetry studies, we find that the fluorinated derivatives exhibit the lowest redox potentials of each of the FcX and fcX2 series. This counterintuitive result is discussed with reference to the spectroscopic, structural, and first-principles calculations of these and related materials.

Palladium‐Catalysed CH Bond Electrophilic Fluorination of Highly Substituted Arylpyrazoles: Experimental and DFT Mechanistic Insights

AbstractA general protocol for palladium‐catalysed CH mono‐ and di‐fluorination of highly substituted arylpyrazoles is reported. Coupling pathways and substrate limitations are discussed in the light of complementary mechanistic experimental and density functional theory (DFT) studies. The mono‐ and di‐ortho‐fluorination of arylpyrazoles having substituted pyrazole groups and ortho‐, meta‐, or para‐substituted arene moieties is achieved. Various pyrazole groups can efficiently promote the direct CH activation/fluorination of substrates bearing valuable reactive ester, cyano, halide and nitro functions. The presence of methoxy, methyl and trifluoromethyl is tolerated on the pyrazole directing groups. However, steric substituent effects have a marked influence which is evidenced by calculations. DFT modelling suggested also a previously unseen outer‐sphere oxidative addition of N‐fluorobenzenesulfonimide (NFSI) to Pd(II) as an alternative mechanism to the commonly assumed Pd(II)/Pd(IV) process. This unprecedented proposal, which is supported by the mass spectrometry identification of a key Pd(II) monomer under the stoichiometric conditions deserves more attention. The influence of elaborate highly substituted directing groups on the course of Pd‐catalysed fluorination has generally received limited attention although this question has a crucial synthetic utility; herein, appropriate conditions for isolating pure products are reported.magnified image

ChemInform Abstract: Radical Decarboxylative Fluorination of Aryloxyacetic Acids Using N‐Fluorobenzenesulfonimide and a Photosensitizer.

Fluorinated methoxy arenes are emerging as important motifs in both agrochemicals and pharmaceuticals. A novel technique for the synthesis of monofluoromethoxy arenes through the direct fluorodecarboxylation of carboxylic acids was developed that uses photosensitizers and N-fluorobenzenesulfonimide (NFSI). Utilization of the oxidatively mild fluorine transfer agent NFSI enabled the synthesis of fluoromethyl ethers that were previously inaccessible with decarboxylative fluorinations performed with Selectfluor. Mechanistic studies are consistent with the photosensitizer effecting oxidation of the aryloxyacetic acid.

ChemInform Abstract: Regioselective Radical Aminofluorination of Styrenes.

The copper-catalyzed radical aminofluorination of styrenes with N-fluorobenzenesulfonimide (NFSI) is realized with high regioselectivity, thus affording aminofluorination products with regioselectivities opposite that of the palladium-catalyzed and noncatalyzed processes. Preliminary mechanistic studies suggested the reaction went through a radical pathway and was supported by DFT calculations. In these reactions, NFSI is utilized as both a radical nitrogen source and radical fluorine source, thus rendering it an attractive reagent.

Radical Decarboxylative Fluorination of Aryloxyacetic Acids Using N‐Fluorobenzenesulfonimide and a Photosensitizer

AbstractFluorinated methoxy arenes are emerging as important motifs in both agrochemicals and pharmaceuticals. A novel technique for the synthesis of monofluoromethoxy arenes through the direct fluorodecarboxylation of carboxylic acids was developed that uses photosensitizers and N‐fluorobenzenesulfonimide (NFSI). Utilization of the oxidatively mild fluorine transfer agent NFSI enabled the synthesis of fluoromethyl ethers that were previously inaccessible with decarboxylative fluorinations performed with Selectfluor. Mechanistic studies are consistent with the photosensitizer effecting oxidation of the aryloxyacetic acid.

N-fluorobenzenesulfonimide based functionalization of C60.

The reaction of N-fluorobenzenesulfonimide (NFSI) with C60 and exploration of the product as a precursor for various 1,2- and 1,4-bisfullerene adducts are reported. NFSI is also found to act as an oxidant in the reaction of C60 with cyclic amines such as pyrrolidine yielding tetraaminoaziridino adducts.

Radical aminooxygenation of alkenes with N-fluoro-benzenesulfonimide (NFSI) and TEMPONa.

Reaction of various alkenes with commercially available N-fluorobenzenesulfonimide (NFSI) and TEMPONa provides the corresponding aminooxygenation products in moderate to good yields. Single electron transfer from readily generated TEMPONa to NFSI allows for clean generation of the corresponding bissulfonylamidyl radical along with TEMPO. N-radical addition to an alkene and subsequent TEMPO trapping provides the corresponding aminooxygenation product.

Reactivity of platinum alkyne complexes towards N-fluorobenzenesulfonimide: formation of platinum compounds bearing a β-fluorovinyl ligand

The platinum(0) alkyne complexes [Pt(L)(η(2)-PhC[triple bond, length as m-dash]CPh)] 1-4 were synthesized by reactions of [Pt(cod)2] with diphenylacetylene and a phosphine ligand precursor (1: L = dcpe, 2: L = xantphos, 3: L = κ(2)-(P,N)-iPr2PC3H6NMe2, 4: L = κ(2)-(P,N)-iPr2PC2H4NMe2). Treatment of 1 or 4 with NFSI gave the complexes [Pt(F){N(SO2Ph)2}(dcpe)] (5) and [Pt(PhC[double bond, length as m-dash]CFPh){N(SO2Ph)2}{κ(2)-(P,N)-iPr2PC2H4NMe2}] (8), whereas the reactivity of 2 and 3 towards NFSI led to product mixtures. The compounds [Pt(F){N(SO2Ph)2}(xantphos)] (6a) as well as [Pt(PhC[double bond, length as m-dash]CFPh){N(SO2Ph)2}{κ(2)-(P,N)-iPr2PC2H4NMe2}] (7a) and [Pt(PhC[double bond, length as m-dash]CFPh)(F){κ(2)-(P,N)-iPr2PC2H4NMe2}] (7b) were clearly identified. Ligand exchange reactions at 8 resulted in the formation of the β-fluorovinyl platinum(ii) complexes [Pt(PhC[double bond, length as m-dash]CFPh){OC(O)CF3}{κ(2)-(P,N)-iPr2PC2H4NMe2}] (9), [Pt(PhC[double bond, length as m-dash]CFPh)(FHF){κ(2)-(P,N)-iPr2PC2H4NMe2}] (10) and [Pt(PhC[double bond, length as m-dash]CFPh)(F){κ(2)-(P,N)-iPr2PC2H4NMe2}] (11). Treatment of 8 with dihydrogen yielded the fluorinated olefin (Z)-(1-fluoroethene-1,2-diyl)dibenzene and [Pt{N(SO2Ph)2}(H){κ(2)-(P,N)-iPr2PC2H4NMe2}] (12).

ChemInform Abstract: Construction of Fluorinated Pyrazole Derivatives via a One‐Pot Tandem C—H Insertion/Electrophilic Fluorination Reaction.

A series of 4-fluoro-pyrazole derivatives were synthesized in moderate to good yields via a one-pot tandem procedure involving an Rh-2(OAc)(4)-catalyzed C-H insertion and an electrophilic fluorination with N-fluorobenzenesulfonimide (NFSI). (C) 2014 Elsevier Ltd. All rights reserved.

A Convenient Preparation of Fluorinating Reagent F‐TEDA Bearing Bisphenylsulfonylimide Counterion and Its Fluorination to Oxindoles

AbstractThe direct preparation of a kind of fluorinating reagent 1 [F‐TEDA‐N(SO2Ph)2] was realized in high yield via the complexation of N‐fluorobenzenesulfonimide (NFSI) with 1‐(chloromethyl)‐1,4‐diazabicyclo[2.2.2]octan‐1‐ium N′,N′‐bis‐(benzenesulfonylimide) salt. In its fluorination to oxindoles, the fluorinating products 6 were afforded in moderate to high yields.

Copper-catalyzed direct amidation of heterocycles with N-fluorobenzenesulfonimide.

A highly efficient amidation reaction of heterocycles with N-fluorobenzenesulfonimide (NFSI) has been developed, presumably proceeding via C-H bond activation. Cuprous iodide was employed as the catalyst, and various α-amidated heterocycle derivatives have been generated in good to excellent yields. This chemistry endowed an economic method of synthesis of valuable amidated heterocycles through a direct C-N bond-coupling processes.

Selectfluor and NFSI exo-glycal fluorination strategies applied to the enhancement of the binding affinity of galactofuranosyltransferase GlfT2 inhibitors.

Two complementary methods for the synthesis of fluorinated exo-glycals have been developed, for which previously no general reaction had been available. First, a Selectfluor-mediated fluorination was optimized after detailed analysis of all the reaction parameters. A dramatic effect of molecular sieves on the course of the reaction was observed. The reaction was generalized with a set of biologically relevant furanosides and pyranosides. A second direct approach involving carbanionic chemistry and the use of N-fluorobenzenesulfonimide (NFSI) was performed and this method gave better diastereoselectivities. Assignment of the Z/E configuration of all the fluorinated exo-glycals was achieved based on the results of HOESY experiments. Furthermore, fluorinated exo-glycal analogues of UDP-galactofuranose were prepared and assayed against GlfT2, which is a key enzyme involved in the cell-wall biosynthesis of major pathogens. The fluorinated exo-glycals proved to be potent inhibitors as compared with a series of C-glycosidic analogues of UDP-Galf, thus demonstrating the double beneficial effect of the exocyclic enol ether functionality and the fluorine atom.

Regioselective radical aminofluorination of styrenes.

The copper-catalyzed radical aminofluorination of styrenes with N-fluorobenzenesulfonimide (NFSI) is realized with high regioselectivity, thus affording aminofluorination products with regioselectivities opposite that of the palladium-catalyzed and noncatalyzed processes. Preliminary mechanistic studies suggested the reaction went through a radical pathway and was supported by DFT calculations. In these reactions, NFSI is utilized as both a radical nitrogen source and radical fluorine source, thus rendering it an attractive reagent.