Enantioselective Intermolecular Radical Amidation and Amination of Benzylic C−H Bonds via Dual Copper and Photocatalysis

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(13)

Published: Feb. 1, 2023

A method for direct access to enantioenriched benzylic amides and carbamate-protected primary benzylamines by C-H functionalization is reported. The substrate used as limiting reagent with only a small excess of the unactivated amide or carbamate nucleophile. enantioselective intermolecular dehydrogenative C-N bond formation enabled combination chiral copper catalyst, photocatalyst, an oxidant, it takes place under mild conditions, which allow broad scope. compatible late-stage functionalization, provides easy 15 N-labeled amines starting from cheap NH4 Cl.

Language: Английский

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Asymmetric sulfonylation with sulfur dioxide surrogates: a new access to enantiomerically enriched sulfones

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(26), P. 3821 - 3826

Published: Jan. 1, 2023

In this highlight, we survey recent exciting advances in asymmetric sulfonylation by using sulfur dioxide surrogates, and discuss induction modes, reaction mechanisms, substrate scope opportunities for further studies.

Language: Английский

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Electron Donor–Acceptor Complex Enabled Cyclization/Sulfonylation Cascade of N-Heterocycles with Thianthrenium Salts

Organic Letters, Journal Year: 2024, Volume and Issue: 26(31), P. 6652 - 6657

Published: July 26, 2024

We report a visible-light-promoted cyclization/sulfonylation cascade of N-heterocycles with thianthrenium salts using DABSO as the SO2 surrogate. This method features excellent functional group tolerance, wide substrate scope, and late-stage elaboration bioactive relevant molecules. Mechanistic investigations reveal that photoactive electron donor–acceptor (EDA) complexes between DABCO are capable generation aryl radicals, which induce following insertion by attacking DABSO, thus triggering key radical cyclization step.

Language: Английский

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Multicomponent Reactions Based on SO₂ Surrogates: Recent Advances

European Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 26(25)

Published: April 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.

Language: Английский

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Photocatalytic Enantioselective Hydrosulfonylation of α,β‐Unsaturated Carbonyls with Sulfonyl Chlorides

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(46)

Published: Oct. 2, 2023

This research explores the enantioselective hydrosulfonylation of various α,β-unsaturated carbonyl compounds via use visible light and redox-active chiral Ni-catalysis, facilitating synthesis enantioenriched α-chiral sulfones with remarkable enantioselectivity (exceeding 99 % ee). A significant challenge entails enhancing reactivity between metal-coordinated moderate electrophilic sulfonyl radicals, aiming to minimize background reactions. The success our approach stems from two distinctive attributes: 1) Cl-atom abstraction employed for radical generation chlorides, 2) single-electron reduction produce a key enolate Ni-complex. latter process appears enhance feasibility radical's addition electron-rich radical. An in-depth investigation into reaction mechanism, supported by both experimental observations theoretical analysis, offers insight intricate process. Moreover, versatility methodology is highlighted through its successful application in late-stage functionalization complex bioactive molecules, demonstrating practicality as strategy producing sulfones.

Language: Английский

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

Organic Letters, Journal Year: 2024, Volume and Issue: 26(15), P. 3321 - 3325

Published: April 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.

Language: Английский

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Multicomponent Sulfonylation of Alkenes to Access β-Substituted Arylsulfones

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(6), P. 3772 - 3780

Published: March 6, 2023

A novel multicomponent sulfonylation of alkenes is described for the assembly various β-substituted arylsulfones using cheap and easily available K2S2O5 as a sulfur dioxide source. Of note, procedure does not need any extra oxidants metal catalysts exhibits relatively wide substrate scope good functional group compatibility. Mechanistically, an initial arylsulfonyl radical formed involving insertion with aryl diazonium salt, followed by alkoxyarylsulfonylation or hydroxysulfonylation alkenes.

Language: Английский

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Copper-Catalyzed 1,4-Trifluoromethylthio-Arylsulfonylation of 1,3-Enynes via the Insertion of Sulfur Dioxide

Organic Letters, Journal Year: 2023, Volume and Issue: 25(31), P. 5916 - 5921

Published: July 27, 2023

A copper-catalyzed trifluoromethylthio-arylsulfonylation between 1,3-enynes, AgSCF3, aryldiazonium tetrafluoroborates, and SO2 (from SOgen) is presented, which could introduce sulfone, SCF3, allene moieties into one molecule simultaneously. This strategy features mild reaction conditions, good substrate compatibility, excellent regioselectivity. The products obtained have the potential for further conversion other valuable compounds. Initial investigations mechanism suggest that it may proceed via a radical pathway. Notably, SOgen was proven as uniquely effective surrogate in this transformation.

Language: Английский

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Visible-Light-Induced Synthesis of Alkylsulfonated Isoquinolinones from 2-Aryl Indoles/Benzimidazoles through Insertion of Sulfur Dioxide

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(13), P. 9293 - 9305

Published: June 7, 2023

A visible-light-induced three-component reaction of 2-aryl indoles/benzimidazoles, Hantzsch esters, and sodium pyrosulfite through a radical cascade cyclization process with the insertion sulfur dioxide is described. It provides novel powerful way for synthesis alkylsulfonated isoquinolinones. esters Na2S2O5 are employed as alkyl precursors SO2 surrogate, respectively. This transformation exhibits good functional group tolerance substrate applicability under mild conditions.

Language: Английский

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Enantioselective sulfonylation using sodium hydrogen sulfite, 4-substituted Hantzsch esters and 1-(arylethynyl)naphthalen-2-ols

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 10(1), P. 92 - 98

Published: Nov. 11, 2022

Synthesis of sulfonyl-containing axially chiral styrenes through a catalytic asymmetric reaction 4-substituted Hantzsch esters, sodium hydrogen sulfite and 1-(arylethynyl)naphthalen-2-ols is reported.

Language: Английский

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