Main Group Redox Catalysis of Organopnictogens: Vertical Periodic Trends and Emerging Opportunities in Group 15

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(4), С. 1699 - 1721

Опубликована: Янв. 19, 2021

A growing number of organopnictogen redox catalytic methods have emerged-especially within the past 10 years-that leverage plentiful reversible two-electron chemistry Group 15. The goal this Perspective is to provide readers context understand dramatic developments in catalysis over decade with an eye toward future development. An exposition fundamental differences atomic structure and bonding pnictogens, thus molecular electronic compounds, presented establish backdrop against which reactivity-and ultimately catalysis-is framed. deep appreciation these underlying periodic principles informs understanding differing modes evokes key challenges field moving forward. We close by addressing forward-looking directions likely animate area years come. What new manifolds can be developed through creative catalyst reaction design that take advantage intrinsic reactivity pnictogens drive discoveries catalysis?

Язык: Английский

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Chiral Hypervalent Iodines: Active Players in Asymmetric Synthesis

Chemical Reviews, Год журнала: 2019, Номер 119(24), С. 12033 - 12088

Опубликована: Ноя. 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.

Язык: Английский

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Progress in organocatalysis with hypervalent iodine catalysts

Chemical Society Reviews, Год журнала: 2022, Номер 51(18), С. 8102 - 8139

Опубликована: Янв. 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.

Язык: Английский

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Recent Developments and Trends in Asymmetric Organocatalysis

European Journal of Organic Chemistry, Год журнала: 2022, Номер 26(1)

Опубликована: Окт. 17, 2022

Asymmetric organocatalysis has experienced a long and spectacular way since the early reports over century ago by von Liebig, Knoevenagel Bredig, showing that small (chiral) organic molecules can catalyze (asymmetric) reactions. This was followed impressive first highly enantioselective in second half of last century, until hype initiated 2000 milestone publications MacMillan List, which finally culminated 2021 Nobel Prize Chemistry. short Perspective aims at providing brief introduction to field looking on historical development more classical methods concepts, discussing selected advanced recent examples opened new directions diversity within this still growing field.

Язык: Английский

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Recent Progress in Synthetic Applications of Hypervalent Iodine(III) Reagents

Chemical Reviews, Год журнала: 2024, Номер unknown

Опубликована: Сен. 13, 2024

Hypervalent iodine(III) compounds have found wide application in modern organic chemistry as environmentally friendly reagents and catalysts. iodine are commonly used synthetically important halogenations, oxidations, aminations, heterocyclizations, various oxidative functionalizations of substrates. Iodonium salts arylating reagents, while iodonium ylides imides excellent carbene nitrene precursors. Various derivatives benziodoxoles, such azidobenziodoxoles, trifluoromethylbenziodoxoles, alkynylbenziodoxoles, alkenylbenziodoxoles group transfer the presence transition metal catalysts, under metal-free conditions, or using photocatalysts photoirradiation conditions. Development hypervalent catalytic systems discovery highly enantioselective reactions chiral represent a particularly recent achievement field chemistry. Chemical transformations promoted by many cases unique cannot be performed any other common, non-iodine-based reagent. This review covers literature published mainly last 7-8 years, between 2016 2024.

Язык: Английский

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Mechanism and Origins of Chemo- and Stereoselectivities of Aryl Iodide-Catalyzed Asymmetric Difluorinations of β-Substituted Styrenes

Journal of the American Chemical Society, Год журнала: 2018, Номер 140(45), С. 15206 - 15218

Опубликована: Окт. 23, 2018

The mechanism of the aryl iodide-catalyzed asymmetric migratory geminal difluorination β-substituted styrenes (Banik et al. Science 2016, 353, 51) has been explored with density functional theory computations. computed consists (a) activation iodoarene difluoride (ArIF2), (b) enantiodetermining 1,2-fluoroiodination, (c) bridging phenonium ion formation via SN2 reductive displacement, and (d) regioselective fluoride addition. According to computational model, ArIF2 intermediate is stabilized through halogen−π interactions between electron-deficient iodine(III) center benzylic substituents at catalyst stereogenic centers. Interactions ester carbonyl groups (I(III)+···O) are not observed in unactivated complex, but do occur upon hydrogen-bonding external Brønsted acid (HF). 1,2-fluoroiodination occurs alkene complexation electrophilic, cationic I(III) followed by C–F bond anti forming C–I bond. bound olefin adopt a spiro arrangement favored transition structures nearly periplanar disfavored structures. Multiple attractive non-covalent interactions, including slipped π···π stacking, C–H···O, C–H···π found underlie high induction. chemoselectivity for 1,1-difluorination versus 1,2-difluorination controlled mainly (1) steric effect substituent on olefinic double (2) nucleophilicity oxygen substrate.

Язык: Английский

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Asymmetric iodine catalysis-mediated enantioselective oxidative transformations

Organic & Biomolecular Chemistry, Год журнала: 2018, Номер 16(30), С. 5386 - 5402

Опубликована: Янв. 1, 2018

The implementation of chiral iodine catalysis has tremendously been developed in the field asymmetric synthesis over past decade.

Язык: Английский

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Catalytic, Enantioselective 1,2-Difluorination of Cinnamamides

Organic Letters, Год журнала: 2019, Номер 21(13), С. 4919 - 4923

Опубликована: Апрель 9, 2019

The enantio- and diastereoselective synthesis of 1,2-difluorides via chiral aryl iodide-catalyzed difluorination cinnamamides is reported. method uses HF-pyridine as a fluoride source mCPBA stoichiometric oxidant to turn over catalyst, affords compounds containing vicinal, fluoride-bearing stereocenters. Selectivity for 1,2-difluorination versus rearrangement pathway resulting in 1,1-difluorination enforced through anchimeric assistance from N- tert-butyl amide substituent.

Язык: Английский

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Recent advances in cellulose supported metal nanoparticles as green and sustainable catalysis for organic synthesis

Cellulose, Год журнала: 2021, Номер 28(8), С. 4545 - 4574

Опубликована: Март 26, 2021

Язык: Английский

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A Triazole‐Substituted Aryl Iodide with Omnipotent Reactivity in Enantioselective Oxidations

Angewandte Chemie International Edition, Год журнала: 2019, Номер 59(4), С. 1479 - 1484

Опубликована: Окт. 10, 2019

Abstract A widely applicable triazole‐substituted chiral aryl iodide is described as catalyst for enantioselective oxidation reactions. The introduction of a substituent in ortho‐position to the key its high reactivity and selectivity. Besides robust modular synthesis, main advantage this excellent performance plethora mechanistically diverse transformations, such spirocyclizations, phenol dearomatizations, α‐oxygenations, oxidative rearrangements. DFT‐calculations situ generated [hydroxy(tosyloxy)iodo]arene isomers give an initial rational observed reactivity.

Язык: Английский

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