Pd(PPh3)4-catalyzed direct ortho-fluorination of 2-arylbenzothiazoles with an electrophilic fluoride N-fluorobenzenesulfonimide (NFSI)

Ding, Qiuping; Ye, Changqing; Pu, Shouzhi; Cao, Banpeng

doi:10.1016/j.tet.2013.11.034

Cited by 49 publications

(26 citation statements)

References 60 publications

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“…A detailed screening of conditions was undertaken (Table S2, Supporting Information). Various F + sources, Pd precursors, acid additives and solvents were tested 17,18. Pd(OAc) 2 in trifluoromethylbenzene (PhCF 3 ) led to 1a in 90% yield.…”

Section: Resultsmentioning

confidence: 99%

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

et al. 2015

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Ag eneral protocolf or palladium-catalysed C À Hm ono-and di-fluorination of highly substituted arylpyrazoles is reported. Coupling pathways and substrate limitations are discussedi nt he light of complementary mechanistic experimental and density functional theory (DFT) studies.T he mono-a nd di-ortho-fluorination of arylpyrazoles having substituted pyrazole groups and ortho-, meta-, or para-substituteda rene moieties is achieved.V arious pyrazole groups can efficiently promote the direct C À Ha ctivation/fluorination of substrates bearing valuable reactive ester, cyano,h alide and nitro functions.T he presence of methoxy,m ethyl and trifluoromethyl is tolerated on the pyrazole directing groups.H owever, steric substituent effects have am arked influence which is evidencedb yc alculations.D FT modelling suggested also ap reviously unseen outer-sphereo xidative addition of N-fluorobenzenesulfonimide (NFSI) to Pd(II) as an alternative mechanism to the commonly assumed Pd(II)/Pd(IV)p rocess.T his unprecedented proposal, which is supported by the mass spectrometry identification of ak ey Pd(II) monomer under the stoichiometric conditions deserves more attention. Thei nfluence of elaborateh ighly substituted directing groups on the course of Pd-catalysed fluorination has generally received limited attentiona lthough this questionh as ac rucial synthetic utility;h erein, appropriate conditions for isolating pure productsare reported.

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Section: Resultsmentioning

confidence: 99%

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

et al. 2015

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“…In 2014, Ding, Pu and co-workers reported a region-selective Pd-catalyzed direct ortho-fluorination of 2-arylbenzothiazoles using N-fluorobenzenesulfonimide (NFSI) as the F + source (Scheme 37). 80 This method provided a facile route to synthesize ortho-fluorinated 2-arylbenzothiazoles 80, which are valuable potential pharmaceuticals and agrochemicals. Though the detailed role of L-proline remains ambiguous, the control experiment showed that L-proline promoted the reaction.…”

Section: Scheme 36 Pd-catalyzed Ortho-acylation With Toluene Derivativesmentioning

confidence: 99%

Recent Advances in the Synthesis and Applications of 2-Arylbenzothiazoles

et al. 2020

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This review firstly covers the applications of 2-arylbenzothiazoles as amyloid imaging agents, antitumor agents, and organic luminescent materials. Then we review the recent advances in the synthesis of 2-arylbenzothiazole derivatives. On the one hand, we introduce the approaches for construction of the 2-arylbenzothiazole core, including the following categories: (i) classic condensation of 2-aminothiophenols, (ii) direct arylation of benzothiazoles, (iii) intramolecular cyclization of thiobenzanilides, and (iv) tandem cyclization of anilines/ nitroarenes with elemental sulfur or sulfides. On the other hand, the transition-metal-catalyzed direct C–H functionalizations of 2-arylbenzothiazoles are also involved in this review.1 Introduction2 Applications of 2-Arylbenzothiazoles3 Construction of the 2-Arylbenzothiazole Core4 Synthesis 2-Arylbenzothiazoles via Direct C–H Functionalization5 Conclusion

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“…69: this problem can be addressed by using the weakly coordinating anionic ortho-directing group N-perfluorotolylamide, which allows for rapid displacement of the monofluorinated product by the substrate, thus affording high selectivity for monofluorination [123][124][125][126]172]. A handful of related Pd-catalyzed electrophilic C-H fluorination reactions have since been reported, for arene substrates with a variety of coordinating directing groups [173][174][175]. While direct C-H fluorination is desirable, the necessity of coordinating has not yet been reported.…”

Section: Fig 58mentioning

confidence: 99%

Transition Metal-Mediated and Metal-Catalyzed Carbon–Fluorine Bond Formation

Campbell

Hoover

Ritter

2014

Topics in Organometallic Chemistry

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The development of new C-F bond forming reactions from organotransition metal complexes has played a key role in advancing the field of fluorination chemistry and has allowed for improved access to fluorinated organic molecules of interest in medicine, materials, and agrochemicals. In this review, we describe the development of transition metal-mediated and metal-catalyzed fluorination methods over the past decade. Special attention is paid to the variety of organometallic mechanisms by which C-F bond formation can occur and the strengths and limitations of different approaches.

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Pd(PPh3)4-catalyzed direct ortho-fluorination of 2-arylbenzothiazoles with an electrophilic fluoride N-fluorobenzenesulfonimide (NFSI)

Cited by 49 publications

References 60 publications

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

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

Recent Advances in the Synthesis and Applications of 2-Arylbenzothiazoles

Transition Metal-Mediated and Metal-Catalyzed Carbon–Fluorine Bond Formation

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