Asymmetric Electrophilic Fluorocyclization with Carbon Nucleophiles

Wolstenhulme, Stephen; Rosenqvist, Jessica; Lozano, O.; Ilupeju, John; Wurz, Nathalie E.; Engle, Keary M.; Pidgeon, George W.; Moore, Peter R.; Sandford, Graham; Gouverneur, Véronique

doi:10.1002/ange.201304845

Cited by 24 publications

(11 citation statements)

References 39 publications

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“…The 1 H NMR spectra were measured with 400 MHz, and 13 C NMR spectra were recorded with 400 (100 MHz), using CDCl 3 as the solvent. 23 N-Benzyl and N-cinnamyl amines were prepared by reaction between commercially available aniline and respective aldehydes using the following standard literature procedure. 24 3,4-Dihydronaphthalen-2-ylmethyl)-aryl amines were prepared by reaction between commercially available anilines and the respective carbaldehyde using the following standard literature procedure.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Highly Selective and Catalytic C–N Bond Cleavage of Tertiary Sulfonamides: Scope and Mechanistic Insight

2021

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A highly chemoselective C–N bond cleavage reaction of p-methoxybenzyl- (PMB), 3,4-dimethoxybenzyl- (DMB), or cinnamyl-substituted tertiary sulfonamides in the presence of catalytic Bi(OTf)3 is presented. A wide range of sulfonamide substrates smoothly furnished the corresponding C–N bond cleavage products in good to excellent yields. Great efforts have been made to obtain insights into the reaction mechanism based on a series of control experiments and mass spectroscopy.

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Section: ■ Experimental Sectionmentioning

confidence: 99%

Highly Selective and Catalytic C–N Bond Cleavage of Tertiary Sulfonamides: Scope and Mechanistic Insight

2021

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“…In 2013, Gouveneur and co‐workers developed a stereoselective method of fluorocyclization for the construction of helical‐shaped tetracyclic structural motifs, 43 and 44 , possessing a fluorine atom at the quaternary stereocenter. For racemic fluorocyclization, various electrophilic fluorinating agents such as Selectfluor, NFSI ( N ‐fluorobenzosulfonimide) and N ‐fluoro‐2,6‐dichloropyridinium triflate 42 were studied.…”

Section: Reaction Classesmentioning

confidence: 99%

Stereoselective Haliranium, Thiiranium and Seleniranium Ion‐Triggered Friedel–Crafts‐Type Alkylations for Polyene Cyclizations

Maji

2019

Adv Synth Catal

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Ther eview is aimeda tdescribingt he advances in electrophilic "iranium" ion-triggered Friedel-Crafts-type alkylation for polyenec yclizations. Owing to the greatp otential of halo-, seleno-and sulfeno-functionalized Friedel-Crafts alkylated compounds,n umerous catalytic methodsh aveb een developed in either racemico re nantiopure forms. More importantly,t hese arene-alkylated or polyenecyclized productsc ontaining halo,s eleno ands ulfeno functionality couldb eu seful in further synthetic planning to access biologically active molecules and natural productsw ith highly complex architectures. Starting from aw ide range of classicalL ewis acids, Brønsted acids and Lewis bases through to the very recently developed halogen bondc atalysts (XB-cat.), selenonium cations as Lewis acids etc. are utilized to access these types of compounds.M orer ecently, some of the co-operative catalytic systems such as phosphite-thiourea, sulfonic acid-phosphoramidite, sulfonic acid-selenophosphoramide,s ulfonic acidanion binding thiourea, etc. catalyzing highly diastereo-and enantioselective polyene cyclizations have also been described. Thec onfigurational stability,r eactivity and selectivity of three-membered cationic

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As af irst example of metal-free and catalytic fluorinative transformationsofalkynes, we developed acycloisomerization-fluorination sequence of N-propargyl amides catalyzed by an iodine(III) species. For the synthesis of fluorinated aliphatic heterocycles, variousm etal-catalyzed intramolecular aminofluorination [3] and oxyfluorinationr eactions [4] of alkenes [5] or their metal-free methods [6,7] have been developed. [1] Accordingly,e fficient introduction methods of fluorine into organic compounds have received much attention recently.

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mentioning

confidence: 99%

“…[1] Accordingly,e fficient introduction methods of fluorine into organic compounds have received much attention recently. For the synthesis of fluorinated aliphatic heterocycles, variousm etal-catalyzed intramolecular aminofluorination [3] and oxyfluorinationr eactions [4] of alkenes [5] or their metal-free methods [6,7] have been developed. For the synthesis of fluorinated aliphatic heterocycles, variousm etal-catalyzed intramolecular aminofluorination [3] and oxyfluorinationr eactions [4] of alkenes [5] or their metal-free methods [6,7] have been developed.…”

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confidence: 99%

Catalytic Cycloisomerization–Fluorination Sequence of N‐Propargyl Amides by Iodoarene/HF⋅Pyridine/Selectfluor Systems

et al. 2016

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As af irst example of metal-free and catalytic fluorinative transformationsofalkynes, we developed acycloisomerization-fluorination sequence of N-propargyl amides catalyzed by an iodine(III) species. The iodine(III) catalyst is in situ generated from iodoarene as aprecatalyst with Selectfluor as af luorinating oxidant in the presence of HF·pyridine.Fluorines ubstituents show am arked improvemento fp roperties, such as solubility,b ioavailability, and metabolic stability, in many examples of introducing fluorine into pharmaceuticals and bioactive substances. [1] Accordingly,e fficient introduction methods of fluorine into organic compounds have received much attention recently. [2] Amongt hem,t he combination of cyclization and fluorination reaction in as ingle operation provides highly efficient approaches to give fluorinated heterocycles from unsaturated compounds bearing ah eteroatom nucleophile. For the synthesis of fluorinated aliphatic heterocycles, variousm etal-catalyzed intramolecular aminofluorination [3] and oxyfluorinationr eactions [4] of alkenes [5] or their metal-free methods [6,7] have been developed. In contrastt ot he reactions of alkenes, the cycloisomerization-fluorination sequence of alkynes has been less studied. [8,9] Althoughg old catalysts with Selectfluor have been well employed for this sequence, the catalytic systemsw ere not effective on that of N-propargyl amides (see the Supporting Information). Also, to the best of our knowledge, metal-free methods for such sequence have not been achievedy et. Moreover,b ecause halocyclization reactions of N-propargyl amides by general halogenating reagents hardly bring about aromatization to halogenated oxazoles, [10] one-pot two-step methods, including metal catalysis for the synthesis of halogenated oxazoles, have been developed by Hashmi's and other groups(Scheme 1a). [10b,c, 11] One the other hand, as part of our studies on the metal-free synthesis of aromatic heterocyclest hrough the activation of alkynes by hypervalent iodine(III) reagents, [12] we have recently found the cycloisomerization-acetoxylation sequence of Npropargyl amides with PhI(OAc) 2 (PIDA) (Scheme 1b). [12a] This reaction, which can afford oxazoles bearing the acetoxyg roup in as ingleo peration, inspired us to examine the formation of fluorinated oxazoles. Herein, ametal-free and catalytic cycloisomerization-fluorinations equence of N-propargyl amides mediated by iodine(III) is described (Scheme 1c).In recent years, there has been ac onsiderable growth in the application of hypervalent iodine reagents to organic syntheses due to their low toxicity and transition-metal-like reactivities, such as an activation of unsaturated bonds, reductive elimination, and ligand exchange. [13] Particularly,( difluoroiodo)arenes (ArIF 2 )c an be used in fluorinative transformations of unsaturated compounds withouta ny metal catalysts. [14] These procedures have been extended to some metal-free cycloisomerization-fluorinationr eactions of alkenes. [15] For example, Hara et al. repo...

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Asymmetric Electrophilic Fluorocyclization with Carbon Nucleophiles

Cited by 24 publications

References 39 publications

Highly Selective and Catalytic C–N Bond Cleavage of Tertiary Sulfonamides: Scope and Mechanistic Insight

Highly Selective and Catalytic C–N Bond Cleavage of Tertiary Sulfonamides: Scope and Mechanistic Insight

Stereoselective Haliranium, Thiiranium and Seleniranium Ion‐Triggered Friedel–Crafts‐Type Alkylations for Polyene Cyclizations

Catalytic Cycloisomerization–Fluorination Sequence of N‐Propargyl Amides by Iodoarene/HF⋅Pyridine/Selectfluor Systems

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