Recent Advances in the Application of Selectfluor as a “Fluorine‐free” Functional Reagent in Organic Synthesis

Yang, Ke; Song, Mengjie; Ali, Ahmed I. M.; Mudassir, Syed M.; Ge, Haibo

doi:10.1002/asia.202000011

Cited by 63 publications

(33 citation statements)

References 83 publications

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“…Synthetically, given the high electronegativity of fluorine, the design of electrophilic fluorine source (F + ) has been more challenging over the years with respect to bromine and chlorine sources. In this sense, Selectfluor ® [ 18 ] ( Figure 2 ) has been groundbreaking, allowing several transformations on alkanes [ 19 ] and aromatic scaffolds [ 20 ]. In regard to the aromatic substrates, electron-donating substituents are known to increase the rate of the formation and yield of fluorinated compounds, obviously [ 21 ].…”

Section: Fluorine and Chlorine In Medicinal Chemistrymentioning

confidence: 99%

New Halogen-Containing Drugs Approved by FDA in 2021: An Overview on Their Syntheses and Pharmaceutical Use

et al. 2022

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This review describes the recent Food and Drug Administration (FDA)-approved drugs (in the year 2021) containing at least one halogen atom (covalently bound). The structures proposed throughout this work are grouped according to their therapeutical use. Their synthesis is presented as well. The number of halogenated molecules that are reaching the market is regularly preserved, and 14 of the 50 molecules approved by the FDA in the last year contain halogens. This underlines the emergent role of halogens and, in particular, of fluorine and chlorine in the preparation of drugs for the treatment of several diseases such as viral infections, several types of cancer, cardiovascular disease, multiple sclerosis, migraine and inflammatory diseases such as vasculitis.

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Section: Fluorine and Chlorine In Medicinal Chemistrymentioning

confidence: 99%

New Halogen-Containing Drugs Approved by FDA in 2021: An Overview on Their Syntheses and Pharmaceutical Use

et al. 2022

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“…In oxidation reactions, selectfluor has frequently combines with transition metal catalysts and photo catalysts [30] . In recent years, selectfluor combines with visible light has significant attention in organic reactions due to N−F of selectfluor could be activated by visible light irradiation to provide N‐radical cation and F radical [31] . These activated radical cation species could effectively activate α C(sp 3 )−H of alcohols, ethers, ketones, esters, thiols and alkyl compounds without photoredox catalysts [32] .…”

Section: Methodsmentioning

confidence: 99%

“…[30] In recent years, selectfluor combines with visible light has significant attention in organic reactions due to NÀ F of selectfluor could be activated by visible light irradiation to provide N-radical cation and F radical. [31] These activated radical cation species could effectively activate α C(sp 3 )À H of alcohols, ethers, ketones, esters, thiols and alkyl compounds without photoredox catalysts. [32] However, to the best of our knowledge, a direct oxidative cyclization of primary alcohol by selectfluor via HAT process has never been explored to date.…”

mentioning

confidence: 99%

Visible‐Light‐Induced Photocatalyst‐Free Oxidative Cyclization of Primary Alcohols by Selectfluor via HAT Process: Synthesis of Quinazolinones and Benzothiadiazines

2021

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A mild and convenient method for oxidative cyclization of primary alcohols with o-aminobenzamides and o-aminobenzenesulfonamides to achieve quinazolinones and benzothiadiazines by selectfluor under visiblelight irradiation was reported. Selectfluor is used as hydrogen atom transfer reagent for oxidative cyclization under visible light irradiation. This photochemical approach offers broad substrate scope of quinazolinones and benzothiadiazines under mild reaction conditions.

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“…Generally, Selectfluor® reacts via 2e À pathways, i. e. it behaves as an oxidant or as an electrophilic fluorine source. [1] However, the 1e À reactivity of Selectfluor® has been gaining increased attention in recent years, as demonstrated by its application as an initiator of radical processes via single electron oxidations, [2] or its involvement in radical fluorination processes. [3] In these reactions, TEDA 2 + * (N-(chloromethyl) triethylenediamine) is generated after the electron or fluorine transfer steps.…”

Section: Introductionmentioning

confidence: 99%

Selectfluor® Radical Dication (TEDA^2+.) – A Versatile Species in Modern Synthetic Organic Chemistry

2020

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In radical processes involving Selectfluor®, TEDA 2 + * (N-(chloromethyl)triethylenediamine) is often generated after an electron or fluorine transfer step. This is a highly reactive species that displays different and unique reactivity when compared to Selectfluor®: It can act as a hydrogen atom transfer (HAT), halogen atom transfer (XAT), or aminating reagent, as well as a powerful single electron oxidant. Despite this versatility, the use of TEDA 2 + * in synthetic processes remains highly underexplored. This minireview, which covers recent applications of TEDA 2 + * to promote a wide range of C-heteroatom and CÀ C bond formations, aims to highlight the potential of this interesting species in organic chemistry. Particular attention is paid to mechanistic aspects involving how TEDA 2 + * is generated and the different reactivity patterns that it can display. TEDA 2 + * as Hydrogen Atom Transfer (HAT) ReagentThe direct functionalization of CÀ H bonds is one of the most attractive strategies for preparing synthetically useful chemicals out of abundant and cheap feedstocks. [4] A key challenge in CÀ H functionalizations is to achieve the selective activation of a given CÀ H bond. Hydrogen atom transfer (HAT) reactions represent a powerful strategy to achieve this goal. [5] One of the main applications of TEDA 2 + * in synthetic organic chemistry is its use as a HAT reagent to facilitate the formation of a wide range of C-heteroatom and CÀ C bonds. Although there are no precise measurements of the properties of TEDA 2 + * as a HAT reagent, based on its reactivity and structure, it can be compared to other amine-based HAT reagents, e. g. quinuclidine. This means that it can selectively activate hydridic CÀ H bonds with BDE � 100 kcal/mol. Csp 3 À F Bond FormationIn 2012, Lectka reported one of the first examples of the use of TEDA 2 + * in HAT processes (Scheme 1). [6] This straightforward fluorination methodology, which enabled the formation of CÀ F bonds from aliphatic, allylic or benzylic CÀ H bonds, required a Cu I catalyst, a radical precursor -N-hydroxyphthalimide (NHPI), a phase transfer catalyst (KB(C 6 F 5 ) 4 ), and Selectfluor® to proceed. Although several mechanistic studies were carried out to [a

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Recent Advances in the Application of Selectfluor as a “Fluorine‐free” Functional Reagent in Organic Synthesis

Abstract: This is the author manuscript accepted for publication and has undergone full peer review but has not been through the copyediting, typesetting, pagination and proofreading process, which may lead to differences between this version and the Version of Record.

Cited by 63 publications

References 83 publications

New Halogen-Containing Drugs Approved by FDA in 2021: An Overview on Their Syntheses and Pharmaceutical Use

New Halogen-Containing Drugs Approved by FDA in 2021: An Overview on Their Syntheses and Pharmaceutical Use

Visible‐Light‐Induced Photocatalyst‐Free Oxidative Cyclization of Primary Alcohols by Selectfluor via HAT Process: Synthesis of Quinazolinones and Benzothiadiazines

Selectfluor® Radical Dication (TEDA^2+.) – A Versatile Species in Modern Synthetic Organic Chemistry

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Recent Advances in the Application of Selectfluor as a “Fluorine‐free” Functional Reagent in Organic Synthesis

Abstract: This is the author manuscript accepted for publication and has undergone full peer review but has not been through the copyediting, typesetting, pagination and proofreading process, which may lead to differences between this version and the Version of Record.

Cited by 63 publications

References 83 publications

New Halogen-Containing Drugs Approved by FDA in 2021: An Overview on Their Syntheses and Pharmaceutical Use

New Halogen-Containing Drugs Approved by FDA in 2021: An Overview on Their Syntheses and Pharmaceutical Use

Visible‐Light‐Induced Photocatalyst‐Free Oxidative Cyclization of Primary Alcohols by Selectfluor via HAT Process: Synthesis of Quinazolinones and Benzothiadiazines

Selectfluor® Radical Dication (TEDA2+.) – A Versatile Species in Modern Synthetic Organic Chemistry

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Product

Resources

About

Selectfluor® Radical Dication (TEDA^2+.) – A Versatile Species in Modern Synthetic Organic Chemistry