Electrochemical Ring-Opening Dicarboxylation of Strained Carbon–Carbon Single Bonds with CO₂: Facile Synthesis of Diacids and Derivatization into Polyesters

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(5), P. 2062 - 2068

Published: Jan. 27, 2022

Diacids are important monomers in the polymer industry to construct valuable materials. Dicarboxylation of unsaturated bonds, such as alkenes and alkynes, with CO2 has been demonstrated a promising synthetic method. However, dicarboxylation C─C single bonds rarely investigated. Herein we report novel electrochemical ring-opening strained rings CO2. Structurally diverse glutaric acid adipic derivatives were synthesized from substituted cyclopropanes cyclobutanes moderate high yields. In contrast oxidative ring openings, this is also first realization an electroreductive reaction rings, including commercialized ones. Control experiments suggested that radical anions carbanions might be key intermediates reaction. Moreover, process features step atom economy, mild conditions (1 atm, room temperature), good chemoselectivity functional group tolerance, low electrolyte concentration, easy derivatization products. Furthermore, conducted polymerization corresponding diesters diols obtain potential UV-shielding material self-healing function fluorine-containing polyester, whose performance tests showed applications.

Language: Английский

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Deconstructive Synthesis of Bridged and Fused Rings via Transition-Metal-Catalyzed “Cut-and-Sew” Reactions of Benzocyclobutenones and Cyclobutanones

Accounts of Chemical Research, Journal Year: 2022, Volume and Issue: 55(16), P. 2341 - 2354

Published: July 28, 2022

ConspectusBridged and fused rings are commonly found in biologically important molecules. Current tactics to construct these ring systems primarily based on stepwise formation (i.e., making one first followed by another) cycloaddition reactions (e.g., Diels–Alder reaction). To seek a complementary perhaps more unified ring-forming approach, deconstructive strategy C–C bond activation of cyclic ketones has been conceived. The named "cut-and-sew" reaction uses with tethered unsaturated moiety as substrates, which involves oxidative addition transition metal into the ketone intramolecular insertion unit. This proved successful access diverse scaffolds that nontrivial otherwise.This Account offers concise summary our laboratory's systematic efforts developing metal-catalyzed cut-and-sew for synthesis bridged over past 10 years. In particular, we will focus using readily available benzocyclobutenones cyclobutanones. date, scope greatly expanded. First, moieties can serve suitable coupling partners, such alkenyl, alkynyl, allenyl, carbonyl, iminyl groups. Second, variety modes have uncovered. this account, (4 + 2), 2 – 1), 1) cycloadditions lead range or be summarized. Third, enantioselective transformations realized efficiently chiral scaffolds, enabled two strategies: enantio-determining migratory desymmetrization Fourth, synthetic applications demonstrated streamlined total syntheses number complex natural products. Compared conventional logics, allows development new bond-disconnecting strategies. Thus, (−)-cycloclavine, (−)-thebainone A, penicibilaenes, proposed cycloinumakiol discussed detail.In narrative chemistry, also aims provide core guiding foundations inspirations toward broader through cleavage. It is anticipated classes compounds could substrates beyond cyclobutanones, coupled. envisaged innovative utilization organic revealed near future.

Language: Английский

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Electrophotochemical Ce-Catalyzed Ring-Opening Functionalization of Cycloalkanols under Redox-Neutral Conditions: Scope and Mechanism

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(30), P. 13895 - 13902

Published: July 21, 2022

Selective cleavage and functionalization of C–C bonds in alcohols is gaining increasing interest organic synthesis biomass conversion. In particular, the development redox-neutral catalytic methods with cheap catalysts clean energy utmost interest. this work, we report a versatile method for ring-opening cycloalkanols by electrophotochemical (EPC) cerium (Ce) catalysis. The EPC-Ce-enabled catalysis allows different ring sizes to be cleaved while tolerating broad range functional groups. Notably, presence chloride as counteranion electrolyte, protocol selectively leads formation C–CN, C–C, C–S, or C–oxime instead C–halide bond after β-scission. A preliminary mechanistic investigation indicates that redox-active Ce catalyst can tuned electro-oxidation photo-reduction, thus avoiding use an external oxidant. Spectroscopic characterizations (cyclic voltammetry, UV–vis, electron paramagnetic resonance, X-ray absorption fine structure) suggest Ce(III)/Ce(IV) pathway transformation, which Ce(IV)-alkoxide involved.

Language: Английский

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Carbon–Carbon Bond Cleavage for Late-Stage Functionalization

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(22), P. 12313 - 12370

Published: Nov. 9, 2023

Late-stage functionalization (LSF) introduces functional group or structural modification at the final stage of synthesis natural products, drugs, and complex compounds. It is anticipated that late-stage would improve drug discovery's effectiveness efficiency hasten creation various chemical libraries. Consequently, products a productive technique to produce product derivatives, which significantly impacts biology development. Carbon-carbon bonds make up fundamental framework organic molecules. Compared with carbon-carbon bond construction, activation can directly enable molecular editing (deletion, insertion, atoms groups atoms) provide more efficient accurate synthetic strategy. However, selective unstrained still one most challenging projects in synthesis. This review encompasses strategies employed recent years for cleavage by explicitly focusing on their applicability functionalization. expands current discourse reactions providing comprehensive overview types bonds. includes C-C(sp), C-C(sp2), C-C(sp3) single bonds; double triple bonds, focus catalysis transition metals organocatalysts. Additionally, specific topics, such as ring-opening processes involving three-, four-, five-, six-membered rings, are discussed, exemplar applications these techniques showcased context bioactive molecules discovery. aims shed light advancements field propose potential avenues future research realm

Language: Английский

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Recent Advances in Electrochemical Carboxylation with CO₂

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: 57(18), P. 2728 - 2745

Published: Sept. 3, 2024

ConspectusCarbon dioxide (CO

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Carbon-carbon triple bond cleavage and reconstitution to achieve aryl amidation using nitrous acid esters

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Jan. 24, 2025

C–C bond cleavage and recombination provide an efficient strategy for the modification reconstruction of molecule structures. Herein, we present a method achieving amidation aryl C(sp2)–H through triple with involvement nitrous acid esters. This marks instance precise controlled stepwise bond, offering fresh perspective such bonds. Nitrous ester serves as both radical source hydrogen atom transfer (HAT) reagent to functionalize utilize two carbon atoms bond. The alkoxy captures from or N-hydroxyl induce 1,3-oxygen migration, which is crucial subsequent molecular authors report achieve bonds by participation

Language: Английский

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Rhodium Catalyzed Regioselective C−H Allylation of Simple Arenes via C−C Bond Activation of Gem‐difluorinated Cyclopropanes

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(19), P. 10626 - 10631

Published: Feb. 18, 2021

Herein, we report a rhodium catalyzed directing-group free regioselective C-H allylation of simple arenes. Readily available gem-difluorinated cyclopropanes can be employed as highly reactive allyl surrogates via sequence C-C and C-F bond activation, providing arene derivatives in good yields with high regioselectivity under mild conditions. The robust methodology enables facile late-stage functionalization complex bioactive molecules. efficiency this reaction is also demonstrated by the turnover number (TON, up to 1700) catalyst on gram-scale experiments. Preliminary success kinetic resolution transformation achieved, promising access enantio-enriched cyclopropanes.

Language: Английский

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A ring expansion strategy towards diverse azaheterocycles

Nature Chemistry, Journal Year: 2021, Volume and Issue: 13(10), P. 1006 - 1016

Published: July 19, 2021

Language: Английский

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Oxime‐Derived Iminyl Radicals in Selective Processes of Hydrogen Atom Transfer and Addition to Carbon‐Carbon π‐Bonds

Advanced Synthesis & Catalysis, Journal Year: 2021, Volume and Issue: 363(10), P. 2502 - 2528

Published: March 25, 2021

Abstract Oximes represent one of the fundamental organic compound classes with a wide range synthetic applications. In last decade O ‐substituted oximes were recognized as synthetically available and versatile precursors iminyl radicals via one‐electron oxidation or reduction employing visible light photoredox catalysts, salts abundant metals (such Cu Fe), other convenient reagents. Iminyl are powerful synthons for various processes cyclization, ring‐opening, CH‐functionalization, coupling. The present review is focused on methods based oxime‐derived developed in few years excluding ring opening reactions cyclic that summarized recent publications. consists two main parts: (1) involving 1,n‐hydrogen atom transfer (n=5 most cases) (2) addition radical to carbon‐carbon π‐bond. magnified image

Language: Английский

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Oxime Ether Synthesis through O–H Functionalization of Oximes with Diazo Esters under Blue LED Irradiation

Organic Letters, Journal Year: 2021, Volume and Issue: 23(17), P. 6951 - 6955

Published: Aug. 12, 2021

A green and sustainable oxime ether formation method via the visible-light-promoted O–H functionalization of oximes with diazo esters is described. The reaction occurs under very mild conditions (catalyst- additive-free) a high yield functional group tolerance. When was performed cyclic as solvent (e.g., THF, 1,4-dioxane, tetrahydropyran, ect.), an interesting photochemical three-component product obtained in good yields.

Language: Английский

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