Methyl NFSI: atom-economical alternative to NFSI shows higher fluorination reactivity under Lewis acid-catalysis and non-catalysis

Fukushi, Kazunobu; Suzuki, Satoru; Kamo, Tomohiro; Tokunaga, Etsuko; Sumii, Yuji; Kagawa, Takumi; Kawada, Kosuke; Shibata, Norio

doi:10.1039/c5gc02612a

Cited by 21 publications

(11 citation statements)

References 46 publications

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“…After a break of a decade, in 2013, chiral dicationic DABCO-based N -F reagents 36-5 and chiral N -fluorobinaphthyldisulfonimides 37-2 were reported by Gouverneur [ 107 ] and by Shibata, Ma, and Cahard [ 108 ], respectively. In 2016, Shibata reported N -fluoromethanesulfonimide (Me-NFSI) as a high atom-economy reagent [ 111 ] and Gouverneur and Cvingroš reported a novel N -F reagent 39-3 derived from the ethylene-bridged Tröger base [ 113 ]. More recently, Zipse and Renaud in 2018, disclosed N -fluoro- N -aryl-arenesulfonamides (NFAS) as radical fluorinating agents [ 115 ].…”

Section: Discussionmentioning

confidence: 99%

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Development of N-F fluorinating agents and their fluorinations: Historical perspective

Umemoto¹,

Yang²,

Hammond³

2021

Beilstein J. Org. Chem.

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This review deals with the historical development of all N-F fluorinating agents developed so far. The unique properties of fluorine make fluorinated organic compounds attractive in many research areas and therefore fluorinating agents are important. N-F agents have proven useful by virtue of their easy handling. This reagent class includes many types of N-F compounds: perfluoro-N-fluoropiperidine, N-fluoro-2-pyridone, N-fluoro-N-alkylarenesulfonamides, N-fluoropyridinium salts and derivatives, N-fluoroquinuclidium salts, N-fluoro-trifluoromethanesulfonimide, N-fluoro-sultams, N-fluoro-benzothiazole dioxides, N-fluoro-lactams, N-fluoro-o-benzenedisulfonimide, N-fluoro-benzenesulfonimide, 1-alkyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane salts, N-fluoropyridinium-2-sulfonate derivatives, 1-fluoro-4-hydroxy-1,4-diazoniabicyclo[2.2.2]octane salts, N-fluorodinitroimidazole, N-fluoro-trichloro-1,3,5-triazinium salt, N-F ethano-Tröger’s base derivatives, N-fluoro-methanesulfonimide, N-fluoro-N-arylarenesulfonamides, bisN-F salts such as N,N’-difluorobipyridinium salts and N,N’-difluoro-1,4-diazoniabicyclo[2.2.2]octane salts, and their many derivatives and analogs, including chiral N-F reagents such as optically active N-fluoro-sultam derivatives, N-fluoro-alkaloid derivatives, DABCO-based N-F derivatives, and N-F binaphthyldisulfonimides. The synthesis and reactions of these reagents are described chronologically and the review also discusses the relative fluorination power of each reagent and their mechanisms chronicling developments from a historical perspective.

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Section: Discussionmentioning

confidence: 99%

“…In 2016, Shibata et al reported the synthesis and reactivity of N -fluoromethanesulfonimide (Me-NFSI, 38-2 ) [ 111 ]. Me-NFSI was first reported in a patent in 1994 [ 112 ], however, the reported fluorinations were vague.…”

Section: Reviewmentioning

confidence: 99%

Development of N-F fluorinating agents and their fluorinations: Historical perspective

Umemoto¹,

Yang²,

Hammond³

2021

Beilstein J. Org. Chem.

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“…For instance, Shibata and co‐workers reported that NFBSI [ N ‐fluoro‐(3,5‐di‐ tert ‐butyl‐4‐methoxy)benzenesulfonimide] as a sterically more demanding NFSI derivative allows the cinchona alkaloid‐catalyzed fluorination of silyl enol ethers to be performed with higher enantioselectivity than in the case of NFSI itself, although the steric hindrance of the former reagent results in decreased reactivity [15] . The above authors also disclosed that the use of a sterically less demanding NFSI derivative (Me‐NFSI) improves reactivity in the Lewis acid‐catalyzed fluorination of β‐keto esters, oxindoles, and malonates [16] . Yang and co‐workers independently reported that in the case of oxindole fluorination, enantioselectivity and reactivity can be increased through the use of structure‐micro‐tuned NFSIs with different substituents on benzene rings [17]…”

Section: Introductionmentioning

confidence: 99%

Bench‐Stable Electrophilic Fluorinating Reagents for Highly Selective Mono‐ and Difluorination of Silyl Enol Ethers

Adachi

Ishibashi²,

Nozaki

et al. 2021

Chemistry A European J

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Efficient methods for the synthesis of fluorinated compounds have been intensively studied, recently. Development of practical fluorinating reagents is indispensable for this purpose. Herein, bench‐stable electrophilic fluorinating reagents were synthesized as N‐fluorobenzenesulfonimide (NFSI) substitutes. Reagents obtained by replacing one of the NFSI sulfonyl groups with an acyl group led to the highly selective monofluorination of silyl enol ethers with suppression of undesired overreaction, that is, difluorination. On the other hand, reagents bearing electron‐withdrawing substituents at NFSI benzenesulfonyl groups efficiently facilitated the difluorination of silyl enol ethers under base‐free conditions. Thus, both mono‐ and difluorinated target materials were prepared from the same substrate.

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“…For example, as presented in Figure 1, 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo [2.2.2]octane bis(tetrafluoroborate) (1), introduced by Professor E. Banks [72], also known as Selectfluor, is one of the best reagents used as a source of "electrophilic fluorine". Other reagents, developed by Professor N. Shibata [73][74][75][76], are N-fluoro-N-(methylsulfonyl)methanesulfonamide (Me-NFSI) (2), 3,5-di-tert-butyl-N-((3,5-di-tert-butyl-4-methoxyphenyl)sulfonyl)-N-fluoro-4-methoxybenzenesulfonamide (NFBSI) (3) and axially chiral NFSIs (4), which can be used for enantioselective fluorination [77]. All these reagents are shelf-stable, easy to handle and operationally convenient to use for various synthetic applications [78][79][80][81].…”

Section: Introductionmentioning

confidence: 99%

Kitamura Electrophilic Fluorination Using HF as a Source of Fluorine

et al. 2020

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This review article focused on the innovative procedure for electrophilic fluorination using HF and in situ generation of the required electrophilic species derived from hypervalent iodine compounds. The areas of synthetic application of this approach include fluorination of 1,3-dicarbonyl compounds, aryl-alkyl ketones, styrene derivatives, α,β-unsaturated ketones and alcohols, homoallyl amine and homoallyl alcohol derivatives, 3-butenoic acids and alkynes.

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Methyl NFSI: atom-economical alternative to NFSI shows higher fluorination reactivity under Lewis acid-catalysis and non-catalysis

Abstract: Me-NFSI is more effective for the fluorination of active methines under Lewis acid-catalysis and non-catalysis than NFSI.

Cited by 21 publications

References 46 publications

Development of N-F fluorinating agents and their fluorinations: Historical perspective

Development of N-F fluorinating agents and their fluorinations: Historical perspective

Bench‐Stable Electrophilic Fluorinating Reagents for Highly Selective Mono‐ and Difluorination of Silyl Enol Ethers

Kitamura Electrophilic Fluorination Using HF as a Source of Fluorine

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