Copper-Catalyzed Chemoselective (Amino)fluorosulfonylation of Hydrocarbons via Intramolecular Fluorine-Atom Transfer

ACS Catalysis, Год журнала: 2024, Номер 14(6), С. 4318 - 4328

Опубликована: Март 6, 2024

Sulfonyl fluorides have found increasing applications as functional molecules in chemistry and biology. We herein report a copper-catalyzed atom-economical access to two categories of sulfonyl through radical relay strategy the presence an SO2 surrogate. The aliphatic C(sp3)–H bond N-fluoro-N-alkyl sulfonamides reacted via 1,5-hydrogen atom transfer (HAT) process, affording alkanesulfonyl with proximal amino group. On other hand, utilizing substrates containing proper C═C double resulted intramolecular olefin aminofluorosulfonylation, allowing synthesis fluorosulfonyl-functionalized pyrrolidines piperidines atom-transfer addition (ATRA). Both reaction systems proceeded under mild conditions, requiring no additional fluorine source. Experimental computational studies suggest that S–F coupling is likely achieved radical-rebound pathway. By taking advantage SuFEx multifunctionality products, method applicable late-stage modification bioactive compounds, drug ligation chemistry, organic synthesis.

Язык: Английский

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Asymmetric Sulfonylation from a Reaction of Cyclopropan-1-ol, Sulfur Dioxide, and 1-(Alkynyl)naphthalen-2-ol

Organic Letters, Год журнала: 2024, Номер 26(15), С. 3321 - 3325

Опубликована: Апрель 10, 2024

Asymmetric sulfonylation from a reaction of cyclopropan-1-ol, sulfur dioxide, and 1-(alkynyl)naphthalen-2-ol in the presence catalytic amount organocatalyst at room temperature is developed. Axially chiral (S)-(E)-1-(1-(alkylsulfonyl)-2-arylvinyl)naphthalen-2-ols are generated moderate to good yields with excellent enantioselectivity regioselectivity under mild conditions. During this transformation, γ-keto sulfinate situ cyclopropan-1-ol dioxide acts as key intermediate.

Язык: Английский

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Copper- and Palladium-Cocatalyzed Chemo-, Regio-, Stereo-, and Atroposelective Arylboration of 1,3-Enynes

ACS Catalysis, Год журнала: 2024, Номер 14(15), С. 11318 - 11331

Опубликована: Июль 15, 2024

Catalytic enantioselective borylation reactions of unsaturated bonds as powerful tools for the synthesis diverse chiral organoboron compounds have gained much attention and wide applications in various fields. However, atroposelective arylboration reaction with carbon–carbon triple 1,3-enynes to obtain axially 1,3-dienylboronates remains an elusive significant challenge. Hence, we develop a cooperative copper- palladium-catalyzed assemble plentiful function enriched single step from easily available 1,3-enynes, B2pin2, aryl bromides high levels chemo-, regio-, stereo-, atroposelectivity. The mild conditions lead good functional group tolerance, which is proven by broad substrate scope late-stage functionalizations bioactive or drug molecules. Moreover, can be scaled up, series further transformations achieved. It worth emphasizing that several olefin catalysts ligands axial chirality also synthesized through corresponding elaborations such products, explains transformative ability application potential 1,3-dienylboronates. mechanism experiment density theory (DFT) calculations revealed process copper palladium catalysis, indicating chemoselectivity regioselectivity boration are determined enyne insertion on copper, atroposelectivity controlled reductive elimination center. Meanwhile, calculation demonstrated distinct interactions between P═O C═O groups Pd Bpin center key transition state formation products varying configurations while employing identical configuration ligands.

Язык: Английский

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Recent advances in organocatalytic atroposelective reactions

Beilstein Journal of Organic Chemistry, Год журнала: 2025, Номер 21, С. 55 - 121

Опубликована: Янв. 9, 2025

Axial chirality is present in a variety of naturally occurring compounds, and becoming increasingly relevant also medicine. Many axially chiral compounds are important as catalysts asymmetric catalysis or have chiroptical properties. This review overviews recent progress the synthesis via organocatalysis. Atroposelective organocatalytic reactions discussed according to dominant catalyst activation mode. For covalent organocatalysis, typical enamine iminium modes presented, followed by N -heterocyclic carbene-catalyzed reactions. The bulk devoted non-covalent activation, where Brønsted acids feature most prolific catalytic structure. last part article discusses hydrogen-bond-donating other motifs such phase-transfer catalysts.

Язык: Английский

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Enantioselective Four-Component Arylsulfonylcyanation of Vinylarenes via the Insertion of SO₂ Enabled by SOgen as SO₂ Surrogate

ACS Catalysis, Год журнала: 2022, Номер 12(17), С. 10764 - 10770

Опубликована: Авг. 18, 2022

A copper-catalyzed four-component enantioselective arylsulfonylcyanation of vinylarenes has been developed that enables easy access to a variety chiral β-sulfonyl nitriles with up 95% yield and 96% ee. The reaction utilizes bench-stable SO2 surrogate (SOgen), takes place under mild conditions, exhibits good substrate scope functional group compatibility. Control experiments show the use SOgen as is key achieving excellent reactivities enantioselectivities. Preliminary mechanistic data indicates this vinylarene 1,2-difunctionalization likely proceeds by radical pathway. exemplifies rare case catalysis involving gaseous SO2.

Язык: Английский

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Photoredox-catalyzed reaction of thianthrenium salts, sulfur dioxide and hydrazines

Organic Chemistry Frontiers, Год журнала: 2022, Номер 9(14), С. 3781 - 3785

Опубликована: Янв. 1, 2022

A photoredox-catalyzed reaction of thianthrenium salts, hydrazines and DABCO·(SO 2 ) is accomplished, providing diverse arenesulfonohydrazides in moderate to good yields under mild conditions.

Язык: Английский

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Construction of sulfonated spiro[5,5]trienones from sulfur dioxide via iron-catalyzed dearomative spirocyclization of biaryls

Organic Chemistry Frontiers, Год журнала: 2022, Номер 9(7), С. 1937 - 1942

Опубликована: Янв. 1, 2022

An iron-catalyzed dearomative spirocyclization of biaryl ynones with sodium metabisulfite and cycloketone oxime esters is developed for the construction sulfonated spiro[5,5]trienones.

Язык: Английский

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Construction of axially chiral compounds via catalytic asymmetric radical reaction

Green Synthesis and Catalysis, Год журнала: 2022, Номер 3(3), С. 212 - 218

Опубликована: Июнь 22, 2022

Язык: Английский

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Multicomponent Reactions Based on SO₂ Surrogates: Recent Advances

European Journal of Organic Chemistry, Год журнала: 2023, Номер 26(25)

Опубликована: Апрель 25, 2023

Abstract Compounds containing sulfonyl‐derived functional groups have received intensive attention owing to their widespread applications in life science, pharmaceuticals and materials science. To access this type of compounds, the multi‐component sulfonylation reactions relying on sulfur dioxide (SO 2 ) insertion strategy emerged as novel attractive approaches past decade. The utilization SO surrogates for multicomponent (MCRs) improved reaction flexibility step economy. Moreover, some advances been achieved challenging but practical asymmetric MCRs construction high value‐added chiral sulfones. This review aims summarize progress made involving from 2019 2022, point out potentials challenges field.

Язык: Английский

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Enantioselective synthesis of chiral sulfones by hydrogen-bonding/organophotoredox co-catalyzed asymmetric sulfonylation

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(9), С. 2251 - 2256

Опубликована: Янв. 1, 2023

We report an enantioselective sulfonylation of α,β-unsaturated carbonyl compounds with 4-alkyl substituted Hantzsch esters and DABCO·(SO 2 ) by interfacing photoredox hydrogen bonding catalysis.

Язык: Английский

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