Asymmetric Intermolecular Iodinative Difunctionalization of Allylic Sulfonamides Enabled by Organosulfide Catalysis: Modular Entry to Iodinated Chiral Molecules

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(36), С. 16490 - 16501

Опубликована: Сен. 2, 2022

Electrophilic halogenation of alkenes is a powerful transformation offering convenient route for the construction valuable functionalized molecules. However, as highly important reaction in this field, catalytic asymmetric intermolecular iodinative difunctionalization remains formidable challenge. Herein, we report that an efficient Lewis basic chiral sulfide-catalyzed approach enables reaction. By approach, challenging substrates such γ,γ-disubstituted allylic sulfonamides and 1,1-disubstituted with sulfonamide unit undergo electrophilic to give variety iodine-functionalized molecules good yields excellent enantio- diastereoselectivities. A series free phenols nucleophiles are successfully incorporated into substrates. Aside from phenols, primary secondary alcohols, fluoride, azide also serve nucleophiles. The obtained iodinated products platform molecule, which can be easily transformed various compounds α-aryl ketones, amines, aziridines via rearrangement or substitution. Mechanistic studies revealed sulfide catalyst displays superior effect on control reactivity iodine enantioselective iodiranium ion intermediate aggregates might formed resting state reactions.

Язык: Английский

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Catalytic Chemo-, Regio-, Diastereo-, and Enantioselective Bromochlorination of Unsaturated Systems Enabled by Lewis Base-Controlled Chloride Release

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(29), С. 13294 - 13301

Опубликована: Июль 12, 2022

A new strategy is described for the Lewis base-catalyzed bromochlorination of unsaturated systems that mechanistically distinct from prior methodologies. The novelty this method hinges on utilization thionyl chloride as a latent source in combination with little 1 mol % triphenylphosphine or oxide basic activators. This metal-free, catalytic chemo-, regio-, and diastereoselective alkenes alkynes exhibits excellent site selectivity polyunsaturated provides access to wide variety vicinal bromochlorides up >20:1 regio- diastereoselectivity. precision installation Br, Cl, I various combinations also demonstrated by simply varying commercial halogenating reagents employed. Notably, when chiral base promoter employed, an enantioselective chalcones possible 92:8 enantiomeric ratio utilizing only 1-3 (DHQD)2PHAL.

Язык: Английский

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Stereospecific syn-dihalogenations and regiodivergent syn-interhalogenation of alkenes via vicinal double electrophilic activation strategy

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Май 2, 2024

Abstract Whereas the conventional anti -dihalogenation of alkenes is a valuable synthetic tool with highly predictable stereospecificity, restricted reaction mechanism makes it challenging to alter diastereochemical course into complementary syn process. Only few notable achievements were made recently by inverting one stereocenters after -addition using carefully designed reagent system. Here, we report conceptually distinctive strategy for simultaneous double electrophilic activation two alkene carbons from same side. Then, resulting vicinal leaving groups can be displaced iteratively nucleophilic halides complete -dihalogenation. For this purpose, thianthrenium dication employed, and all possible combinations chlorine bromine are added onto internal successfully, particularly in -dibromination regiodivergent -bromochlorination.

Язык: Английский

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Phosphorus(III)-Mediated, Tandem Deoxygenative Geminal Chlorofluorination of 1,2-Diketones

Organic Letters, Год журнала: 2020, Номер 22(11), С. 4190 - 4195

Опубликована: Май 8, 2020

Tetrasubstituted carbon containing two different halogen substituents was constructed in a single-step operation by utilizing the carbene-like reactivity of dioxaphospholene through tandem reaction electrophilic and nucleophilic halogenating reagents. It crucial to devise non-dealkylatable phosphoramidite, which enabled efficient formation geminal chlorofluorides from various 1,2-diketones with (PhSO2)2NF n-Bu4NCl. In addition, selective functionalization chlorine substituent demonstrated, absence scrambling confirmed.

Язык: Английский

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The applications of catalytic asymmetric halocyclization in natural product synthesis

Organic Chemistry Frontiers, Год журнала: 2021, Номер 9(2), С. 499 - 516

Опубликована: Ноя. 18, 2021

Catalytic asymmetric halocyclization of olefinic substrate has evolved rapidly and been well utilized as a practical strategy for constructing enantioenriched cyclic skeletons in natural product synthesis.

Язык: Английский

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Photoredox synthesis of Vicinal Dichloride using FeCl₃ as chlorine source

Asian Journal of Organic Chemistry, Год журнала: 2023, Номер 12(6)

Опубликована: Май 2, 2023

Abstract This work presents a photo‐redox vicinal dichlorination of acrylamides using naturally abundant chlorine source (FeCl 3 ). The LMCT FeCl is responsible for the radical inducement, while tetra‐ n ‐butylammonium decatungstate (TBADT) catalytic system enhanced process. method exhibits extraordinarily mild conditions, not requiring external ligands and low E factors, which enables scalable synthesis.

Язык: Английский

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A dynamic picture of the halolactonization reaction through a combination of ab initio metadynamics and experimental investigations

Chemical Science, Год журнала: 2021, Номер 12(22), С. 7746 - 7757

Опубликована: Янв. 1, 2021

Ab initio dynamics of the halolactonization reaction provide insights into diastereoselectivity reaction. Noncovalent interactions between substrate, halogen source and solvent are revealed to direct formation syn-product.

Язык: Английский

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Visible‐Light‐Induced Vicinal Dichlorination of Alkenes through LMCT Excitation of CuCl₂

Angewandte Chemie, Год журнала: 2020, Номер 132(52), С. 23809 - 23814

Опубликована: Сен. 27, 2020

Abstract This work demonstrates photoredox vicinal dichlorination of alkenes, based on the homolysis CuCl 2 in response to irradiation with visible light. catalysis proceeds via a ligand metal charge transfer process and provides an exciting opportunity for synthesis 1,2‐dichloride compounds using inexpensive, low‐molecular‐weight chlorine source. new exhibits wide substrate scope, excellent functional group tolerance, extraordinarily mild conditions does not require external ligands. Mechanistic studies show that ready formation atom radicals is responsible facile C−Cl bonds this synthetic process.

Язык: Английский

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Recent advances in versatile pyridazine-cored materials: principles, applications, and challenges

Journal of Materials Chemistry C, Год журнала: 2023, Номер 11(17), С. 5563 - 5584

Опубликована: Янв. 1, 2023

Advances in versatile pyridazine-based materials for optoelectronics, chromism, sensing, catalysis, and energy storage/release, etc. , are reviewed.

Язык: Английский

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Carbene-Catalyzed [4+2] Cycloaddition of Cyclobutenones and Isatins for Quick Access to Chiral Chlorine-Containing Spirocyclic δ-Lactones

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(10), С. 7286 - 7294

Опубликована: Май 2, 2024

Here we report a carbene-catalyzed enantio- and diastereoselective [4+2] cycloaddition reaction of cyclobutenones with isatins for the quick efficient synthesis spirocyclic δ-lactones bearing chiral chlorine. A broad range substrates various substitution patterns proceed smoothly in this reaction, spirooxindole δ-lactone products afforded generally good to excellent yields optical purities under mild conditions.

Язык: Английский

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