Positional and Geometrical Isomerisation of Alkenes: The Pinnacle of Atom Economy

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(39), P. 13654 - 13664

Published: June 25, 2019

Strategies to achieve spatiotemporal regulation of pre-existing alkenes via external stimuli are essential given the ubiquity feedstock olefins in chemistry and their downstream applications. Mirroring 1-0 switch that underpins mammalian vision through selective geometric isomerisation retinal, strategies manipulate 2D space by both positional chemical, thermal light-driven processes being intensively pursued. This minireview highlights current state art activating achieving directionality these fundamental chemical transformations.

Language: Английский

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Where Does the Fluorine Come From? A Review on the Challenges Associated with the Synthesis of Organofluorine Compounds

Organic Process Research & Development, Journal Year: 2020, Volume and Issue: 24(4), P. 470 - 480

Published: March 5, 2020

Fluorinated organic molecules are increasingly being prepared for a variety of applications, including pharmaceutical products. However, the supply chain to access necessary raw materials, which originate primarily from calcium fluoride, is often not considered, may be difficult at commercial scale, and has become destabilized as more stringent environmental policies justifiably enforced. This manuscript presents an overview preparation use simple organofluorinated intermediates reagents challenges associated with them.

Language: Английский

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Chiral Hypervalent Iodines: Active Players in Asymmetric Synthesis

Chemical Reviews, Journal Year: 2019, Volume and Issue: 119(24), P. 12033 - 12088

Published: Nov. 19, 2019

Asymmetric organocatalytic oxidations have been witnessed to an impressive development in the last years thanks establishment of important chiral hypervalent iodines(III/V). Many different approaches involving both stoichiometric and catalytic versions provided a fundamental advance this area within asymmetric synthesis. The easily handing, nontoxic, mild, environmentally friendly (green oxidants), high stability that are features these reagents applied many reactions also allowed exploring further unprecedented enantioselective transformations. intention present review is thus highlight as whole utilized up date prepare iodines(III/V), well their reactivity comprehensive manner.

Language: Английский

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Progress in organocatalysis with hypervalent iodine catalysts

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(18), P. 8102 - 8139

Published: Jan. 1, 2022

Hypervalent iodine compounds as environmentally friendly and relatively inexpensive reagents have properties similar to transition metals. They are employed alternatives metal catalysts in organic synthesis mild, nontoxic, selective recyclable catalytic reagents. Formation of C-N, C-O, C-S, C-F C-C bonds can be seamlessly accomplished by hypervalent catalysed oxidative functionalisations. The aim this review is highlight recent developments the utilisation iodine(III) iodine(V) a wide range including chiral for stereoselective synthesis. Polymer-, magnetic nanoparticle- framework-supported also described.

Language: Английский

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Strategies for Nucleophilic C(sp³)–(Radio)Fluorination

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(18), P. 9928 - 9950

Published: April 24, 2023

This Perspective surveys the progress and current limitations of nucleophilic fluorination methodologies. Despite long rich history C(sp3)–F bond construction in chemical research, inherent challenges associated with this transformation have largely constrained to a privileged reaction platform. In recent years, Doyle group─along many others─has pursued study development intent generating deeper mechanistic understanding, developing user-friendly reagents, contributing invention synthetic methods capable enabling radiofluorination. Studies from our laboratory are discussed along developments others field. Fluoride reagent implications identity highlighted. We also outline space inaccessible by technologies series future directions field that can potentially fill existing dark spaces.

Language: Английский

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Systematic Investigation of Lipophilicity Modulation by Aliphatic Fluorination Motifs

Journal of Medicinal Chemistry, Journal Year: 2020, Volume and Issue: 63(3), P. 1002 - 1031

Published: Jan. 2, 2020

Optimization of compound lipophilicity is a key aspect drug discovery. The aim this work was to compare the modulations induced by 16 distinct known and novel fluoroalkyl motifs on three parent models. Fifty fluorinated compounds, with 28 experimental aliphatic log P values, are involved in discussing various trends. As well as confirming trends, number lipophilicity-reducing introduced. Tactics reduce discussed, such "motif extensions" rearrangements", including concomitant extension carbon chain, one- two-fluorine 'deletions' within perfluoroalkyl groups. Quantum chemical calculations (SMD-MN15) based solvent-dependent three-dimensional (3D) conformational analysis gave excellent correlations superior Clog predictions 2D structural motifs. availability systematic collection data small molecules illustrates relative fluorination

Language: Английский

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Electrochemical Vicinal Difluorination of Alkenes: Scalable and Amenable to Electron‐Rich Substrates

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 59(3), P. 1155 - 1160

Published: Nov. 7, 2019

Fluorinated alkyl groups are important motifs in bioactive compounds, positively influencing pharmacokinetics, potency and conformation. The oxidative difluorination of alkenes represents an strategy for their preparation, yet current methods limited alkene-types tolerance electron-rich, readily oxidized functionalities, as well safety scalability. Herein, we report a method the number unactivated that is tolerant electron-rich functionality, giving products otherwise unattainable. Key to success electrochemical generation hypervalent iodine mediator using "ex-cell" approach, which avoids substrate decomposition. more sustainable conditions give good excellent yields up decagram scales.

Language: Английский

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Fluorination and Fluoroalkylation Reactions Mediated by Hypervalent Iodine Reagents

Advanced Synthesis & Catalysis, Journal Year: 2020, Volume and Issue: 362(20), P. 4256 - 4292

Published: Aug. 4, 2020

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

Language: Английский

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Expanding organofluorine chemical space: the design of chiral fluorinated isosteres enabled by I(i)/I(iii) catalysis

Chemical Science, Journal Year: 2021, Volume and Issue: 12(32), P. 10686 - 10695

Published: Jan. 1, 2021

Short aliphatic groups are prevalent in bioactive small molecules and play an essential role regulating physicochemistry molecular recognition phenomena.

Language: Английский

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Regio‐ and Enantioselective Intermolecular Aminofluorination of Alkenes via Iodine(I)/Iodine(III) Catalysis**

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(32)

Published: May 18, 2022

The regio- and enantio-selective, intermolecular vicinal fluoroamination of α-trifluoromethyl styrenes has been achieved by enantioselective I

Language: Английский

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