Ritter-enabled catalytic asymmetric chloroamidation of olefins DOI Creative Commons

Daniel C. Steigerwald,

Bardia Soltanzadeh,

Aritra Sarkar

et al.

Chemical Science, Journal Year: 2020, Volume and Issue: 12(5), P. 1834 - 1842

Published: Dec. 8, 2020

Intermolecular asymmetric haloamination reactions are challenging due to the inherently high halenium affinity (HalA) of nitrogen atom, which often leads N-halogenated products as a kinetic trap. To circumvent this issue, acetonitrile, possessing low HalA, was used nucleophile in catalytic Ritter-type chloroamidation allyl-amides. This method is compatible with Z and E alkenes both alkyl aromatic substitution. Mild acidic workup reveals 1,2-chloroamide enantiomeric excess greater than 95% for many examples. We also report successful use sulfonamide chlorenium reagent dichloramine-T chlorenium-initiated reaction. Facile modifications lead chiral imidazoline, guanidine, orthogonally protected 1,2,3 tri-amines.

Language: Английский

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

Xinru Xu,

Jieying Ji

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(36), P. 16490 - 16501

Published: Sept. 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.

Language: Английский

Citations

22
Catalytic Chemo-, Regio-, Diastereo-, and Enantioselective Bromochlorination of Unsaturated Systems Enabled by Lewis Base-Controlled Chloride Release DOI Creative Commons

Alexandra E. Lubaev,

Manjula D. Rathnayake,

Favour Eze

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(29), P. 13294 - 13301

Published: July 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.

Language: Английский

Citations

20
Stereospecific syn-dihalogenations and regiodivergent syn-interhalogenation of alkenes via vicinal double electrophilic activation strategy DOI Creative Commons
Hyeon Moon, Jungi Jung, Jun‐Ho Choi

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: May 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.

Language: Английский

Citations

3
Phosphorus(III)-Mediated, Tandem Deoxygenative Geminal Chlorofluorination of 1,2-Diketones DOI
Garam Choi, Ha Eun Kim,

Sunjoo Hwang

et al.

Organic Letters, Journal Year: 2020, Volume and Issue: 22(11), P. 4190 - 4195

Published: May 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.

Language: Английский

Citations

26
The applications of catalytic asymmetric halocyclization in natural product synthesis DOI

Jiahang Yan,

Zhiqiang Zhou,

Qiaoqiao He

et al.

Organic Chemistry Frontiers, Journal Year: 2021, Volume and Issue: 9(2), P. 499 - 516

Published: Nov. 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.

Language: Английский

Citations

21
Photoredox synthesis of Vicinal Dichloride using FeCl3 as chlorine source DOI

Xinren Wang,

Changyi Shi,

Mengyu Yang

et al.

Asian Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 12(6)

Published: May 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.

Language: Английский

Citations

6
A dynamic picture of the halolactonization reaction through a combination of ab initio metadynamics and experimental investigations DOI Creative Commons
Ruben Van Lommel, Jonathan Bock, Constantin G. Daniliuc

et al.

Chemical Science, Journal Year: 2021, Volume and Issue: 12(22), P. 7746 - 7757

Published: Jan. 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.

Language: Английский

Citations

12
Visible‐Light‐Induced Vicinal Dichlorination of Alkenes through LMCT Excitation of CuCl2 DOI

Pengcheng Lian,

Wenhao Long,

Jingjing Li

et al.

Angewandte Chemie, Journal Year: 2020, Volume and Issue: 132(52), P. 23809 - 23814

Published: Sept. 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.

Language: Английский

Citations

12
Recent advances in versatile pyridazine-cored materials: principles, applications, and challenges DOI
Jing Zhang,

Yanze Jiang,

Xiaojie Cheng

et al.

Journal of Materials Chemistry C, Journal Year: 2023, Volume and Issue: 11(17), P. 5563 - 5584

Published: Jan. 1, 2023

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

Language: Английский

Citations

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

Xian Zhou,

Qinqin Liu

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(10), P. 7286 - 7294

Published: May 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.

Language: Английский

Citations

1