Halogenation of Alkenes Using Three‐Component Reactions: A Decade of Development DOI

Rongliang Zeng,

Li Zhang, Dayun Huang

et al.

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: May 23, 2024

Abstract Alkenes are valuable feedstocks in organic synthesis. One effective method for synthesizing halides with functional groups close proximity involves the direct difunctionalization of alkenes via three‐component reactions. This approach not only reduces number steps involved synthesis process, but also minimizes waste generation and enables formation complex molecules from simple starting materials. In this review, we mainly discuss decade developments (2013‐2023) two categories: (1) halogenation three‐membered ring intermediates, involving haliranium, thiiranium,seleniranium, aziridinium epoxide species; (2) a radical pathway. Reactions I 2 , BiI 3 NaI, Bu 4 N + [I(O CAr) ] − NIS, NBS, NCS, DBH, BsNMeBr, HBr, HCl, KI, NH I, O 5 Et ⋅ 3HF, Selectfluor, CuI, CuBr, CuCl, LiCl, KBr, NaCl, SOCl Py 9HF, NFSI, TBSCl et al have been recorded how added reagents work will be discussed. We hope review do help future research area.

Language: Английский

Telluronium‐Catalyzed Halogenation Reactions: Chalcogen‐Bond Activation of N‐Halosuccinimides and Catalysis DOI Creative Commons

Loïc Groslambert,

Patrick Pale, Victor Mamane

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(43)

Published: May 24, 2024

The ability of triaryltelluronium salts to interact with N-halosuccinimides (NXS) through chalcogen bonding (ChB) in the solid state and solution is demonstrated herein. Cocrystals bearing two CF

Language: Английский

Citations

5
Catalytic Enantioselective Friedel–Crafts Reactions of Arenes Enabled by Iranium/Irenium-Ion-Triggered Electrophilic Functionalization DOI
Yuanyuan Zhang, Shuai Ding,

Limin Meng

et al.

Synlett, Journal Year: 2025, Volume and Issue: unknown

Published: April 14, 2025

Abstract The catalytic asymmetric Friedel–Crafts reactions of (hetero)arenes represent a cornerstone in synthetic chemistry due to their ability efficiently incorporate aromatic rings into complex molecular architectures. This account presents comprehensive overview recent advancements the enantioselective (hetero)arenes, with particular focus on that facilitate introduction multiple C–C bonds via iranium/irenium-ion-triggered electrophilic processes. We examine detail strategies and methodologies employed achieve stereoselective incorporation unsaturated bonds, highlighting construction diverse structural scaffolds. Additionally, this showcases broad range applications powerful transformation organic synthesis. 1 Introduction 2 Catalytic Enantioselective Reactions Thiiranium/Thiirenium Ions 2.1 Arylthiiranium/Arylthiirenium-Ion-Triggered 2.2 Trifluoromethylthiiranium/Trifluoromethylthiirenium-Ion-Triggered 3 Haliranium 3.1 Chloriranium-Ion-Triggered 3.2 Bromiranium-Ion-Triggered 3.3 Iodiranium-Ion-Triggered Asymmetric Oxidative Arylation Alkenes 4 Conclusion Outlook

Language: Английский

Citations

0
Recent progress in the organoselenium-catalyzed difunctionalization of alkenes DOI
Pei Qu, Gong‐Qing Liu

Organic & Biomolecular Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Selenium-based catalysts have recently been utilized to facilitate a variety of new organic transformations, owing their intrinsic advantages, including low cost, toxicity, stability in both air and water, strong compatibility with diverse functional groups. The difunctionalization alkenes-the process incorporating two groups onto carbon-carbon double bond-has garnered particular interest within the chemical community its significant applications synthesis. Recently, organoselenium-catalyzed alkenes has emerged as an ideal powerful route obtain high-value vicinal difunctionalized molecules. This review emphasizes recent advancements this rapidly evolving field, focusing on scope, limitations, mechanisms various reactions.

Language: Английский

Citations

0
A Theoretical Study on the Mechanism of Bifunctional Brønsted Acid/Base-Catalyzed CO2-Fixation Reaction with Homoallylic Amine DOI
Yu Wang, Xin Zhang, Jia Zhou

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 90(6), P. 2172 - 2179

Published: Jan. 31, 2025

The reaction mechanism and the enantioselectivity of Brønsted acid/base (trans-stilbene diamine, simplified by BAM)-catalyzed CO2 fixation with homoallylic amine have been investigated using density functional theory (DFT) calculations. proposed involves initial activation acid, followed nucleophilic attack on to form a carbamate intermediate. base subsequently deprotonates intermediate cyclic product, regenerating acid catalyst. C-O cyclization is enantio-determining step. hydrogen bond network formed catalyst substrate, similar an enzyme pocket, plays key role in stereoselectivity. In addition, energy decomposition analysis (EDA) confirms that bonding driven orbital electrostatic attractions. more basic BAM (OMe at quinoline 7-position) exhibits enhanced enantioselectivity.

Language: Английский

Citations

0
Asymmetric Halocyclization of 2-Anilidostyrenes Using N-Haloamides Enabled by Chiral Anion Phase-Transfer Catalysis DOI
Penghui Zhang, Xue Du, Guo-Gang Tu

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 31, 2025

Asymmetric halogenation for efficient construction of various 4H-3,1-benzoxazine derivatives with excellent functional group tolerance using readily available N-haloamides as the halogen source and ammonium phosphate salt catalyst under mild reaction conditions has been developed. The loading could be reduced to 1 mol % recycled 4 times without deterioration in reactivity stereoselectivity. Importantly, this process features a column-purification-free operation, leading green atom-economical preparation chiral benzoxazines good yields high enantioselectivities.

Language: Английский

Citations

0
Dielectrophilic Approach to Sequential Heterofunctionalization of Ethylene from Vinylthianthrenium Salt DOI Creative Commons
Giandomenico Magagnano, Valentin Poirier, Filippo Romoli

et al.

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(21)

Published: April 2, 2024

Abstract Vinyl thianthrenium salt is a compound with interesting electrophilic properties capable of reacting two distinct nucleophiles. By using β‐keto esters as one the reaction partners, it possible to insert chain carbon atoms further functionalization under mild conditions. We have studied this new methodology which involves stepwise formation C−C and C−X bond (with X=N, O, etc.) in step without use metals. Depending on conditions starting ketoester, varied reactivity has been observed described.

Language: Английский

Citations

2
Palladium/Xu-Phos-catalyzed enantioselective arylalkoxylation reaction of γ-hydroxyalkenes at room temperature DOI
Shuai Zhu, Mingjie Chen,

Haichao Shen

et al.

Chinese Chemical Letters, Journal Year: 2024, Volume and Issue: 35(11), P. 109879 - 109879

Published: April 10, 2024

Language: Английский

Citations

1
Chiral non Aromatic Nitrogen-Heterocycles by Asymmetric Intramolecular Haloamination and Haloamidation DOI Open Access
Mario Orena

Published: May 27, 2024

This review deals with the functionalization of double bonds carried out in presence a chiral catalyst exploiting intramolecular attack to haliranium ions by nucleophilic nitrogen amides or carbamates prepared from achiral aminoalkenes, and C-N formation leads highly enantioenriched non-aromatic heterocycles. A range protocols are reported, emphasizing synthesis many natural biologically active products pharmacological interest according this methodology.

Language: Английский

Citations

1
Chiral Nonaromatic Nitrogen-Heterocycles by Asymmetric Intramolecular Haloamination and Haloamidation DOI Creative Commons
Mario Orena, Samuele Rinaldi

Organics, Journal Year: 2024, Volume and Issue: 5(3), P. 163 - 204

Published: July 2, 2024

This review deals with the functionalization of double bonds carried out in presence a chiral catalyst exploiting intramolecular attack to haliranium ions by nucleophilic nitrogen amides or carbamates prepared from achiral aminoalkenes, and C–N formation leads highly enantioenriched nonaromatic heterocycles. A range protocols are reported, emphasizing synthesis many natural biologically active products pharmacological interest according this methodology.

Language: Английский

Citations

0
Enantioselective Construction of Axially Iodobenzocarbazole Derivatives by Stereogenic‐at‐Cobalt(III)‐Complex‐Catalyzed Iodoarylation of Alkynes DOI
Chuan‐Zhi Yao, Ziyuan Zhao,

Xue‐Qin Tu

et al.

European Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 26(42)

Published: Sept. 7, 2023

Abstract A new synthetic approach to novel axially chiral iodobenzocarbazole derivatives based on the highly enantioselective intramolecular iodoarylation of linked alkyne‐indole systems was developed by using versatile catalyst, stereogenic‐at‐cobalt(III)‐complex, through an iodinated vinylidene o ‐quinone methide (IVQM) intermediate. This protocol provides 21 examples in excellent yields with good high enantioselectivities (up 96 % yield, 98 ee). Furthermore, introduced iodine atoms can easily be converted into other functional groups.

Language: Английский

Citations

1