Dynamism of Supramolecular DNA/RNA Nanoarchitectonics: From Interlocked Structures to Molecular Machines

Bulletin of the Chemical Society of Japan, Год журнала: 2020, Номер 93(4), С. 581 - 603

Опубликована: Фев. 10, 2020

Abstract In order to fabricate highly sophisticated nanostructures, various research fields must be fused into one unified concept. recently emerging nanoarchitectonics, nanotechnology is combined with materials science, supramolecular self-assembly, and biological science construct functional from nanoscale units. This review article focuses on dynamic features of nanoarchitectonics. terms this concept, molecular machines as the forefront targets are produced DNA RNA. Fundamental designs DNA/RNA first described an emphasis significant roles interlocked structures such rings, catenanes, rotaxanes, connectors these parts. latter part, including shuttles, transporters, walkers, nano pumps, robots, amplifiers, logic gates presented, together related functions sensitive sensing catalysis regulation. The exemplified strategy should universally useful which fulfill social demands at present well in future.

Язык: Английский

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Photoinduced Three-Component Difluoroalkylation of Quinoxalinones with Alkenes via Difluoroiodane(III) Reagents

Organic Letters, Год журнала: 2022, Номер 24(19), С. 3576 - 3581

Опубликована: Май 12, 2022

An environmentally friendly strategy for the photocatalyzed three-component reaction between quinoxalinones, alkenes, and hypervalent iodine(III) reagents is disclosed. The new designed difluoroiodane(III) reagent shows excellent reactivity, providing a wide range of difluoroalkyl-substituted quinoxaline-2(1H)-ones in moderate to yields under mild conditions. Experimental studies demonstrated that difluoroalkyl radical intermediate was involved this reaction.

Язык: Английский

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Organo-mediator enabled electrochemical transformations

Chemical Society Reviews, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

This review highlights organo-mediators that enable electrochemical reactions via outer-sphere electron transfer (ET), offering advantages such as availability, tunability, and simplified post-processing compared to direct electrolysis.

Язык: Английский

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Catalytic Cleavage of C(sp²)–C(sp²) Bonds with Rh-Carbynoids

Journal of the American Chemical Society, Год журнала: 2019, Номер 141(39), С. 15509 - 15514

Опубликована: Сен. 12, 2019

We report a catalytic strategy that generates rhodium-carbynoids by selective diazo activation of designed carbyne sources. found rhodium-carbynoid species provoke C(sp2)–C(sp2) bond scission in alkenes inserting monovalent carbon unit between both sp2-hybridized carbons. This skeletal remodeling process accesses synthetically useful allyl cation intermediates conduct to valuable allylic building blocks upon nucleophile attack. Our results rely on the formation cyclopropyl-I(III) able undergo electrocyclic ring-opening, following Woodward–Hoffmann–DePuy rules.

Язык: Английский

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Electrogenerated hypervalent iodine compounds as mediators in organic synthesis

Current Opinion in Electrochemistry, Год журнала: 2019, Номер 15, С. 83 - 88

Опубликована: Март 29, 2019

Язык: Английский

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Mechanism and Origins of Enantioselectivities in Spirobiindane-Based Hypervalent Iodine(III)-Induced Asymmetric Dearomatizing Spirolactonizations

Journal of the American Chemical Society, Год журнала: 2019, Номер 141(40), С. 16046 - 16056

Опубликована: Сен. 13, 2019

The work of Kita et al. on asymmetric oxidative dearomatization naphthol carboxylic acids to spirolactones mediated/catalyzed by a novel, conformationally rigid μ-oxo-bridged hypervalent iodine(III) species is landmark discovery in enantioselective catalysis [Kita, Y.; Angew. Chem., Int. Ed. 2008, 47, 3787. DOI: 10.1002/anie.200800464; J. Am. Chem. Soc. 2013, 135, 4558. 10.1021/ja401074u]. We have investigated the detailed mechanism this important transformation using density functional theory. Calculations revealed that proton transfer from pendant acid naphthols bridging oxygen atom or ligand species, which enhances nucleophilicity and nucleofugality iodoarene, crucial for dearomatizing spirolactonization. Halogen bonding between resulting carboxylate electron-deficient center further stabilizes spirolactonization transition states. also long-neglected cleaved μ-oxo more reactive but less selective than itself naphthols. coexistence two sequential processes reaction system results lower enantioselectivity. A new stereochemical model able reproduce rationalize observed apparent enantioselectivities proposed.

Язык: Английский

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Enantioselective Construction of Tertiary Fluoride Stereocenters by Organocatalytic Fluorocyclization

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(47), С. 20048 - 20057

Опубликована: Ноя. 16, 2020

1,1-Disubstituted styrenes with internal oxygen and nitrogen nucleophiles undergo oxidative fluorocyclization reactions in situ generated chiral iodine(III)-catalysts. The resulting fluorinated tetrahydrofurans pyrrolidines contain a tertiary carbon–fluorine stereocenter. Application of new 1-naphthyllactic acid-based iodine(III)-catalyst allows the control stereocenters up to 96% ee. Density functional theory calculations are performed investigate details mechanism factors governing stereoselectivity reaction.

Язык: Английский

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Photocatalytic Fluoro Sulfoximidations of Styrenes

Angewandte Chemie International Edition, Год журнала: 2020, Номер 59(33), С. 14134 - 14137

Опубликована: Май 16, 2020

Abstract Reactions of difluoroiodotoluene with NH‐sulfoximines provide new hypervalent iodine(III) reagents, which photocatalytically transfer a fluoro and sulfoximidoyl group onto styrenes high regioselectivity. The substrate scope is broad respect to both sulfoximines olefins. Following an operationally simple protocol, large library fluorine‐containing N‐functionalized can be accessed. Results from mechanistic investigations revealed the importance radical intermediates.

Язык: Английский

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Catalytic Enantioselective Synthesis of Difluorinated Alkyl Bromides

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(35), С. 14831 - 14837

Опубликована: Авг. 17, 2020

We report an iodoarene-catalyzed enantioselective synthesis of β,β-difluoroalkyl bromide building blocks. The transformation involves oxidative rearrangement α-bromostyrenes, utilizing HF–pyridine as the fluoride source and m-CPBA stoichiometric oxidant. A catalyst decomposition pathway was identified, which, in tandem with structure–activity relationship studies, facilitated development improved providing higher enantioselectivity lower loadings. versatility difluoroalkyl products demonstrated via highly enantiospecific substitution reactions suitably reactive nucleophiles. origins were investigated using computed interaction energies simplified substrate structures, evidence for both CH−π π–π transition state interactions critical features.

Язык: Английский

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Chiral phosphoric acid catalyzed aminative dearomatization of α-naphthols/Michael addition sequence

Nature Communications, Год журнала: 2019, Номер 10(1)

Опубликована: Июль 17, 2019

Asymmetric dearomatization reactions have recently emerged as a powerful tool for the rapid build-up of molecular complexity. Chiral three-dimensional polycyclic molecules bearing contiguous stereogenic centers can be synthesized from readily available planar aromatic feedstocks. Here we report that an intermolecular asymmetric reaction α-naphthols tethered nucleophile at C4 position naphthol ring is achieved by chiral phosphoric acid. The proceeds via highly chemo- and regioselective aminative dearomatization/Michael addition sequence, affording wide array functionalized cyclic ketones in good yields (up to 93%) with excellent enantioselectivity >99% ee). catalyst loading reduced 0.1 mol%. Preliminary mechanistic investigations identify established step, while Michael rate-limiting step. A working model accounting origin stereochemistry proposed based on DFT calculations.

Язык: Английский

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