Hypervalent Iodine/HF Reagents for the Synthesis of 3-Fluoropyrrolidines

Kitamura, Tsugio; Miyake, Azusa; Muta, Kensuke; Oyamada, and Juzo

doi:10.1021/acs.joc.7b01266

Cited by 46 publications

(20 citation statements)

References 38 publications

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“…[12] Thechemotherapeutic potential of (+ +)-Catechin (4) [13] further adds to this clinical diversity (Figure 1, top). To reconcile the clinical importance of chromanes,a nd the potential of bioisosterism, with the value of catalysis-based strategies to access enantioenriched 3-fluoro scaffolds,aformal 6-endo-trig fluorocyclization [14,15] of simple allyl phenyl ethers via I I /I III catalysis [16] was envisaged (Figure 1, bottom). This conceptually simple entry point would likely accelerate investigation of the physicochemical profile inherent to this intriguing 3D drug module.…”

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confidence: 99%

Enantioselective Synthesis of 3‐Fluorochromanes via Iodine(I)/Iodine(III) Catalysis

et al. 2020

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The chromane nucleus is common to a plenum of bioactive small molecules where it is frequently oxidized at position 3. Motivated by the importance of this position in conferring efficacy, and the prominence of bioisosterism in drug discovery, an iodine(I)/iodine(III) catalysis strategy to access enantioenriched 3‐fluorochromanes is disclosed (up to 7:93 e.r.). In situ generation of ArIF2 enables the direct fluorocyclization of allyl phenyl ethers to generate novel scaffolds that manifest the stereoelectronic gauche effect. Mechanistic interrogation using deuterated probes confirms a stereospecific process consistent with a type IIinv pathway.

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confidence: 99%

Enantioselective Synthesis of 3‐Fluorochromanes via Iodine(I)/Iodine(III) Catalysis

et al. 2020

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“…Moreover, intramolecular aminofluorination of homoallylamine derivatives (69) with PhI(OAc) 2 and pyridine • HF at room temperature gave N-tosyl-3fluoropyrrolidines (70) in good to high yields. [31] A catalytic aminofluorination method was also achieved by using p-iodotoluene as a catalyst, pyridine • HF as a fluorine source, and m-CPBA as a terminal oxidant (Scheme 14). This reaction was applicable to fluorocyclization of the substrates with oxygen nucleophiles, e. g., homoallylalcohols and butenoic acid.…”

Section: Amino- Oxy-or Carbofluorination Of Alkenesmentioning

confidence: 99%

“…The aminofluorination might proceed through two possible pathways (Scheme 14). [31] In path a, the in situ formed difluoroiodobenzene is activated by HF and attacks the CÀ C double bond of 69 a to generate 71. Then, 71 undergoes ring-opening through attack of the terminal carbon by the nucleophilic nitrogen atom to afford 72, which is subject to S N 2-type substitution and deprotonation to form 3-fluoropyrrolidines (70 a).…”

Section: Amino- Oxy-or Carbofluorination Of Alkenesmentioning

confidence: 99%

Fluorination and Fluoroalkylation Reactions Mediated by Hypervalent Iodine Reagents

Han

Zhang

2020

Adv Synth Catal

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This review summarizes the progress in the fluorination and fluoroalkylation of electron-rich systems with diverse fluorine (F) and fluoroalkyl (R fn) reagents employing hypervalent iodine compounds as initiators in the last few decades. Because of the strong electrophilicity, high oxidizing properties, low toxicity, air and moisture stability, ready availability, ease of handling, and mild reaction conditions, the hypervalent iodine reagents have been widely utilized in modern organic chemistry. In particular, the use of hypervalent iodine reagents to initiate the CÀ F and CÀ R fn (R fn =CF 2 H, CF 3 , perfluoroalkyl, OCH 2 CF 3 , SCF 3 , SeCF 3 and etc) bond formation has been increasingly developed. In these reactions, hypervalent iodine compounds behave as powerful oxidants or electrophiles and activate the fluorination/fluoroalkylation reagents, the transitionmetal catalysts, or the substrates to in situ form electrophilic or radical intermediates, which subsequently participate in fluorination, difluoromethylation, trifluoromethylation, perfluoroalkylation, trifluoroethoxylation, fluoroalkylthiolation, trifluoromethylselenolation and others under mild conditions. Although great achievements have been made in this area, they are just the initial phase and still require a wide scope for improvement. It is anticipated that this review will draw much attention from the organic chemistry community and inspire more contributions in the development of new hyper-valent-iodine-mediated fluorination and fluoroalkylation reactions.

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“…[12] Das chemotherapeutische Potenzial von (+ +)-Catechin (4) [13] unterstreicht diese Bandbreite klinischer Wirkungsbereiche noch zusätzlich (Abbildung 1, oben). Es wurde angenommen, dass eine formale 6-endo-trig-Fluorzyklisierung [14,15] einfacher Allylphenylether durch I I /I III -Katalyse [16] die klinische Wichtigkeit der Chromane und das Potential der Bioisosterie mit der Bedeutung Katalyse-basierter Strategien zur Synthese des enantiomerenangereicherten 3-Fluorgerüsts zusammenführt (Abbildung 1, unten). Dieser konzeptionell einfache Einstiegspunkt wird sehr wahrscheinlich die Erforschung des physikochemikalischen Profils dieses interessanten 3D-Wirkstoffmoduls beschleunigen.…”

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Enantioselektive Synthese von 3‐Fluorchromanen durch Iod(I)/Iod(III)‐Katalyse

et al. 2020

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Das Chromangerüst findet sich in einer Vielzahl von kleinen, bioaktiven Molekülen, in denen die 3‐Position häufig oxidiert wird. Motiviert durch die Wichtigkeit dieser Position für die Wirksamkeit sowie die Bedeutung der Bioisosterie in der Wirkstoffforschung wurde eine Iod(I)/Iod(III)‐Katalysestrategie für den Zugang zu enantiomerenangereicherten 3‐Fluorchromanen entwickelt (bis zu 7:93 e.r.). Die In‐situ‐Erzeugung von ArIF2 ermöglicht die direkte Fluorzyklisierung von Allylphenylethern, um neue Molekülgerüste zu erzeugen, die den stereoelektronischen gauche‐Effekt zeigen. Mechanistische Untersuchungen unter Verwendung von deuterierten Substraten bestätigen einen stereospezifischen Prozess, der mit einem Reaktionsverlauf des Typs IIinv übereinstimmt.

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Hypervalent Iodine/HF Reagents for the Synthesis of 3-Fluoropyrrolidines

Cited by 46 publications

References 38 publications

Enantioselective Synthesis of 3‐Fluorochromanes via Iodine(I)/Iodine(III) Catalysis

Enantioselective Synthesis of 3‐Fluorochromanes via Iodine(I)/Iodine(III) Catalysis

Fluorination and Fluoroalkylation Reactions Mediated by Hypervalent Iodine Reagents

Enantioselektive Synthese von 3‐Fluorchromanen durch Iod(I)/Iod(III)‐Katalyse

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