Radical transformations for allene synthesis

Chemical Science, Год журнала: 2022, Номер 13(29), С. 8491 - 8506

Опубликована: Янв. 1, 2022

Allenes are valuable organic molecules that feature unique physical and chemical properties. They not only often found in natural products, but also act as versatile building blocks for the access of complex molecular targets, such pharmaceuticals, functional materials. Therefore, many remarkable elegant methodologies have been established synthesis allenes. Recently, more methods radical allenes developed, clearly emphasizing associated great synthetic values. In this perspective, we will discuss recent important advances

Язык: Английский

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Organoselenium Compounds: Chemistry and Applications in Organic Synthesis

Chemistry - A European Journal, Год журнала: 2023, Номер 29(52)

Опубликована: Июнь 28, 2023

Abstract Selenium, originally described as a toxin, turns out to be crucial trace element for life that appears selenocysteine and its dimer, selenocystine. From the point of view drug developments, selenium‐containing drugs are isosteres sulfur oxygen with advantage presence selenium atom confers antioxidant properties high lipophilicity, which would increase cell membrane permeation leading better oral bioavailability. In this article, we have focused on relevant features atom, above all, corresponding synthetic approaches access variety organoselenium molecules along proposed reaction mechanisms. The preparation biological selenosugars, including selenoglycosides, selenonucleosides, selenopeptides, other compounds will treated. We attempted condense most important aspects interesting examples chemistry into single article.

Язык: Английский

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Carbon–Carbon Bond Cleavage for Late-Stage Functionalization

Chemical Reviews, Год журнала: 2023, Номер 123(22), С. 12313 - 12370

Опубликована: Ноя. 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

Язык: Английский

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Photoredox-Catalyzed α-Sulfonylation of Ketones from Sulfur Dioxide and Thianthrenium Salts

Organic Letters, Год журнала: 2022, Номер 24(15), С. 2955 - 2960

Опубликована: Апрель 13, 2022

A photoredox-catalyzed sulfonylation of silyl enol ethers with DABCO·(SO2)2 and thianthrenium salts is achieved, providing diverse β-keto sulfones in moderate to good yields. This protocol features easily accessible starting materials functional group compatibility, enabling the introduction various functionalized sulfonyl groups into ketones. Furthermore, as one important industrial raw materials, methanol can be employed methyl source prepare α-methylsulfonated ketones through a intermediate for first time.

Язык: Английский

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An iron-catalyzed multicomponent reaction of cycloketone oxime esters, alkenes, DABCO·(SO₂)₂ and trimethylsilyl azide

Organic Chemistry Frontiers, Год журнала: 2022, Номер 9(4), С. 917 - 922

Опубликована: Янв. 1, 2022

The synthesis of β-azidosulfones starting from alkenes, cycloketone oxime esters, trimethylsilyl azide and a sulfur dioxide surrogate DABCO·(SO 2 ) under iron catalysis is developed.

Язык: Английский

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Synthesis of Sulfilimines via Aryne and Cyclohexyne Intermediates

Organic Letters, Год журнала: 2023, Номер 25(27), С. 5157 - 5161

Опубликована: Июль 5, 2023

An efficient and metal-free approach for the synthesis of sulfilimines from sulfenamides with aryne cyclohexyne precursors has been developed. The reaction proceeds through unusual S–C bond formation, which offers a novel practical entry to access wide range in moderate good yields excellent chemoselectivity. Moreover, this protocol is amenable gram-scale applicable transformation products into useful sulfoximines.

Язык: Английский

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Metal-Free Chemoselective S-Arylation of Sulfenamides To Access Sulfilimines

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(13), С. 9352 - 9359

Опубликована: Июнь 16, 2023

A novel and efficient S-arylation of sulfenamides with diaryliodonium salts for the synthesis sulfilimines is developed. The reaction proceeds smoothly under transition-metal-free air conditions, giving rapid access to in good excellent yields via selective S-C bond formation. This protocol scalable exhibits a broad substrate scope, functional group tolerance, chemoselectivity.

Язык: Английский

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Regioselective Hydro(deutero)silylation of 1,3-Enynes Enabled by Photoredox/Nickel Dual Catalysis

Organic Letters, Год журнала: 2024, Номер 26(2), С. 536 - 541

Опубликована: Янв. 5, 2024

In the presence of visible light irradiation, organophoto/nickel dual catalysts, and mild base K2HPO4, 1,3-enynes react with silanecarboxylic acids to give corresponding α-silylallenes high selectivity. this uniquely decarboxylative hydrosilylation 1,3-enynes, a silyl radical process is involved diverse electron-rich -poor substrates proceed smoothly in moderate excellent yields. This transformation particularly synthetically worthwhile when using MeOD as solvent, which furnishes new access α-silyldeuteroallenes.

Язык: Английский

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Nickel-Catalyzed Reaction between Vinyl Azides and an Alkyl Sulfonyl Radical Generated from DMSO: Rapid Access to β-Keto Sulfones

ACS Sustainable Chemistry & Engineering, Год журнала: 2024, Номер 12(12), С. 5046 - 5051

Опубликована: Март 14, 2024

A sustainable method for the construction of valuable β-keto sulfones lies in reaction between vinyl azides and alkyl sulfonyl radical generated from low-cost comparatively steady bulk chemical dimethyl sulfoxide (DMSO) that has been developed. This strategy features mild economical conditions using inexpensive NiCl2 as catalyst H2O2 green oxidant. The conversion occurs through a sequence ordered processes consisting addition, denitrogen, hydrogen abstraction, hydrolysis. Mechanistic studies indicate sulfinic acid produced DMSO plays an essential role reduction Ni(III). sensitivity assessment gram-scale experiments proceed smoothly to demonstrate robustness practicality this protocol.

Язык: Английский

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N-Heterocyclic Carbene-Catalyzed 1,4-Alkylacylation of 1,3-Enynes

Organic Letters, Год журнала: 2021, Номер 23(23), С. 9251 - 9255

Опубликована: Ноя. 17, 2021

The radical relay coupling reaction recently emerged as a powerful synthetic strategy for producing tetrasubstituted allenes. However, bond-forming processes involving the allenyl intermediate are mostly limited to those promoted by transition metals. In this report, we describe that ketyl generated from single-electron oxidation of Breslow is an excellent partner radicals. An organocatalytic 1,4-alkylacylation 1,3-enynes occurred smoothly in presence aldehyde, precursor, and N-heterocyclic carbene catalyst. This transformation showed remarkable tolerance both aromatic aliphatic aldehydes, enyne substitution, diversified precursors.

Язык: Английский

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