Three-membered cyclic fluoronium ions in gaseous ion-neutral complexes

Nguyen, Viet; Cheng, Xueheng; Morton, Thomas Hellman

doi:10.1021/ja00044a026

Cited by 41 publications

(25 citation statements)

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“…Fluorine cannot form uoriranium ions, excluding a reaction path involving such an ion. [57][58][59][60] NFSI proved to be much less reactive and the reaction could only be observed at RT in MeCN. 61,62 Nevertheless, uorolactonization proceed under these conditions in acceptable yield (62%) and with decent diastereoselectivity (d.r.…”

Section: Resultsmentioning

confidence: 99%

A dynamic picture of the halolactonization reaction through a combination of ab initio metadynamics and experimental investigations

et al. 2021

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Section: Resultsmentioning

confidence: 99%

A dynamic picture of the halolactonization reaction through a combination of ab initio metadynamics and experimental investigations

et al. 2021

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“…Fluoronium ions are highly unstable, owing to the extremely high electronegativity of fluorine (electronegativity 4.0 on the Pauling scale). The best evidence of fluoronium ions was first obtained in the gas phase by mass spectrometric experiments . However, in 2013, Lectka and co‐workers reported the generation of transient fluoronium ion 1 in the solution phase (Scheme ) …”

Section: Classical Use Of Halonium Ions and Commercially Availablementioning

confidence: 99%

Role of Lewis‐Base‐Coordinated Halogen(I) Intermediates in Organic Synthesis: The Journey from Unstable Intermediates to Versatile Reagents

et al. 2017

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The widespread use of halogen‐based reagents in organic synthesis is well known. Hypervalent halogens (oxidation states III and V) have been explored to a significant extent. Among them, hypervalent iodine reagents have found major use and applications. In contrast, understanding of the reactivity of halogen(I) species in the presence of Lewis bases, and their reaction mechanisms, are very limited. This microreview sheds light on the importance of halogen(I) species and their applications in organic synthesis. In commercially available halogen(I) precursors such as N‐halosuccinimides, the halogen atom is attached to the nitrogen atom through a covalent bond with low electrophilicity and thus low reactivity. Interestingly, the reactivity increases if the electrophilic halogen(I) atom is attached to a Lewis base through a polarized covalent bond. The halogen‐bonding interaction between the Lewis base and the halonium ion (or halonium ion equivalent) results in highly reactive and thermodynamically stable halogen(I) intermediates that act as versatile reagents. This microreview unravels the evolution of the unstable halogen(I) intermediates to become versatile reagents.

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“…Interestingly, these stoichiometric methods usually employed chinchona alkaloids in monomeric or dimeric form to complex the fluorinating agent and induce chirality. For example, Selectfluor in combination with an acylated dihydroquinine was used for the enantioselective fluorination of silyl enol ethers;6a,b (DHQ) 2 PYR and Selectfluor were used for the fluorination of allylsilanes;6c and quinine and Selectfluor induced enantioselective semipinacol rearrangement in cyclohexene derivatives 6d. Stoichiometric asymmetric fluorocyclizations of allylsilanes are also possible if (DHQ) 2 PHAL is used together with Selectfluor 6e…”

Section: Catalytic Asymmetric Fluorinations Of Alkenesmentioning

confidence: 99%

“…This will also include a summary of the recent mechanistic work on the electrophilic halogenation of alkenes, although it has to be said that the mechanistic understanding of many of the new catalyst systems is still only preliminary. The discussion will mainly focus on the “heavier” halogens chlorine, bromine, and iodine as their electrophilic chemistry towards alkenes is distinctly different from fluorine, which, unlike the other halogens, does generally not react via a cyclic halonium ion‐like species 6. New methods for the catalytic, enantioselective addition of fluorine to alkenes will be therefore covered in a separate section at the end of this article.…”

Section: Introductionmentioning

confidence: 99%

New Catalytic Approaches towards the Enantioselective Halogenation of Alkenes

Hennecke

2012

Chemistry An Asian Journal

233

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The addition of electrophilic reagents to the carbon-carbon double bond is one of the most fundamental reactions in organic chemistry. Halogen electrophiles constitute probably the most important class of electrophiles and have been widely used to induce electrophilic addition reactions to alkenes like halolactonizations or dihalogenations. Despite their long history and high importance, catalytic, asymmetric variants of these reactions have been underdeveloped until very recently. During the last two years this has changed and many novel approaches have been reported. This review aims to cover these new developments through discussing the common themes as well as the suggested mechanistic scenarios.

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Three-membered cyclic fluoronium ions in gaseous ion-neutral complexes

Cited by 41 publications

References 0 publications

A dynamic picture of the halolactonization reaction through a combination of ab initio metadynamics and experimental investigations

A dynamic picture of the halolactonization reaction through a combination of ab initio metadynamics and experimental investigations

Role of Lewis‐Base‐Coordinated Halogen(I) Intermediates in Organic Synthesis: The Journey from Unstable Intermediates to Versatile Reagents

New Catalytic Approaches towards the Enantioselective Halogenation of Alkenes

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