Nickel-Catalyzed Selective C–H Cyanation via Aromatic Thianthrenium Salts DOI
Guofu Zhang, Zijin Luo, Chenfei Guan

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(13), P. 9249 - 9256

Published: June 23, 2023

Here, we report the first case of nickel-catalyzed C–H cyanation via arylthianthrenium salts. The reaction features use air-stable and inexpensive NiCl2·6H2O as a catalyst for highly selective construction products by aromatic pre-thianthrenation. mechanism study shows that formation aryl radicals is involved. Also, this protocol can be applied to late-stage functionalization bioactive molecules readily scalable, further showcasing synthetic utility.

Language: Английский

Organothianthrenium salts: synthesis and utilization DOI Creative Commons
Huan Meng, Ming‐Shang Liu, Wei Shu

et al.

Chemical Science, Journal Year: 2022, Volume and Issue: 13(46), P. 13690 - 13707

Published: Jan. 1, 2022

This review summarizes the synthesis of diverse organothianthrenium salts from various precursors and their applications in organic to forge new C–C, C–H C–heteroatom bonds by C–S bond cleavage with different mechanistic considerations.

Language: Английский

Citations

133

An electron donor–acceptor photoactivation strategy for the synthesis of S-aryl dithiocarbamates using thianthrenium salts under mild aqueous micellar conditions DOI
Hao Xu, Xufeng Li, Jie Ma

et al.

Chinese Chemical Letters, Journal Year: 2023, Volume and Issue: 34(11), P. 108403 - 108403

Published: March 30, 2023

Language: Английский

Citations

53

Transition-metal-free C–S bond cleavage and transformation of organosulfur compounds DOI
Ke Yang, Qin Li, Zhengyi Li

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(36), P. 5343 - 5364

Published: Jan. 1, 2023

The activation and transformation of organic chemical bonds is a fundamental scientific problem. In the past several decades, C-S bond cleavage for construction C-C C-heteroatom has received tremendous attention in chemistry. Although significant progress been made field transition metal strategies, variety novel transition-metal-free strategies have also developed using halogenated reagents, oxidants, acids, bases. Moreover, photochemical electrochemical methods to achieve organosulfur compounds. To date, however, no comprehensive review reported. Therefore, we herein provide major advances compounds, including thioethers, sulfoxides, sulfones, thioacetals, sulfonium salts, sulfur ylides.

Language: Английский

Citations

44

Arylthianthrenium Salts as the Aryl Sources: Visible Light/Copper Catalysis-Enabled Intermolecular Azidosulfonylation of Alkenes DOI
Hao Xu, Xufeng Li, Yifei Wang

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(9), P. 1845 - 1850

Published: Feb. 26, 2024

The difunctionalization of alkenes using aryl thianthrenium salts as the sources has been reported sporadically. However, four-component on basis not thus far and still remains a challenge. Herein, visible light/copper catalysis-enabled reaction salts, DABCO·(SO

Language: Английский

Citations

26

Unified metal-free intermolecular Heck-type sulfonylation, cyanation, amination, amidation of alkenes by thianthrenation DOI Creative Commons
Ming‐Shang Liu,

Hai‐Wu Du,

Huan Meng

et al.

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

Published: Jan. 15, 2024

Abstract Direct and site-selective C-H functionalization of alkenes under environmentally benign conditions represents a useful attractive yet challenging transformation to access value-added molecules. Herein, unified protocol for variety intermolecular Heck-type functionalizations C sp2 -H bond has been developed by thianthrenation. The reaction features metal-free operationally simple exclusive cine -selective aliphatic aryl forge C-C, C-N, C-P, C-S bonds at room temperature, providing general with nucleophiles (Nu = sulfinates, cyanides, amines, amides). Alkenes undergo -sulfonylation, cyanation, amination afford alkenyl sulfones, nitriles enamines.

Language: Английский

Citations

22

Intermolecular Metal‐Free Cyclopropanation and Aziridination of Alkenes with XH2(X=N, C) by Thianthrenation** DOI
Ming‐Shang Liu,

Hai‐Wu Du,

Jian‐Fang Cui

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(41)

Published: Aug. 17, 2022

Three-membered cyclic structures are widely existing in natural products and serve as enabling intermediates organic synthesis. However, the efficient straightforward access to such with diversity remains a formidable challenge. Herein, general practical protocol aziridines cyclopropanes synthesis using free XH2 (X=C or N) alkenes by thianthrenation is presented. This metal-free features direct aziridination cyclopropanation unprotected . Free sulfonamides, amides, carbamates, amines, methylene acidic protons, good precursors, providing an attractive alternative for of from easily available starting materials.

Language: Английский

Citations

52

Regiospecific Alkene Aminofunctionalization via an Electrogenerated Dielectrophile DOI
Dylan E. Holst, Céline Dorval,

Casey K. Winter

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(15), P. 8299 - 8307

Published: April 6, 2023

Modular strategies to rapidly increase molecular complexity have proven immensely synthetically valuable. In principle, transformation of an alkene into a dielectrophile presents opportunity deliver two unique nucleophiles across alkene. Unfortunately, the selectivity profiles known dielectrophiles largely precluded this deceptively simple synthetic approach. Herein, we demonstrate that dicationic adducts generated through electrolysis alkenes and thianthrene possess profile relative more conventional dielectrophiles. Specifically, these species undergo single perfectly regioselective substitution reaction with phthalimide salts. This observation unlocks appealing new platform for aminofunctionalization reactions. As illustrative example, implement reactivity paradigm address longstanding challenge: diamination distinct nitrogen nucleophiles. Studies mechanism process reveal key alkenyl thianthrenium salt intermediate controls exquisite regioselectivity highlight importance proton sources in controlling sulfonium electrophiles.

Language: Английский

Citations

34

Photocatalyst/metal-free sequential C–N/C–S bond formation: Synthesis of S-arylisothioureas via photoinduced EDA complex activation DOI

Guoju Guo,

Xufeng Li, Jie Ma

et al.

Chinese Chemical Letters, Journal Year: 2024, Volume and Issue: 35(11), P. 110024 - 110024

Published: May 17, 2024

Language: Английский

Citations

18

Photocatalytic Functionalization of Dehydroalanine‐Derived Peptides in Batch and Flow DOI Creative Commons
Nikolaos Kaplaneris, Merve Akdeniz, Méritxell Fillols

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(19)

Published: March 18, 2024

Abstract Unnatural amino acids, and their synthesis by the late‐stage functionalization (LSF) of peptides, play a crucial role in areas such as drug design discovery. Historically, LSF biomolecules has predominantly utilized traditional synthetic methodologies that exploit nucleophilic residues, cysteine, lysine or tyrosine. Herein, we present photocatalytic hydroarylation process targeting electrophilic residue dehydroalanine (Dha). This possesses an α , β ‐unsaturated moiety can be combined with various arylthianthrenium salts, both batch flow reactors. Notably, setup proved instrumental for efficient scale‐up, paving way unnatural acids peptides substantial quantities. Our approach, being inherently mild, permits diversification even when they contain sensitive functional groups. The readily available salts facilitate seamless integration Dha‐containing wide range arenes, blueprints, natural products, culminating creation unconventional phenylalanine derivatives. synergistic effect high group tolerance modular characteristic aryl electrophile enables peptide conjugation ligation conditions.

Language: Английский

Citations

17

Alkene Thianthrenation Unlocks Diverse Cation Synthons: Recent Progress and New Opportunities DOI Creative Commons
Min Ji Kim, Karina Targos, Dylan E. Holst

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(16)

Published: Feb. 8, 2024

Oxidative alkene functionalization reactions are a fundamental class of complexity-building organic transformations. However, the majority established approaches rely on electrophilic reagents that limit diversity groups can be installed. Recent advances have new approach instead relies transformation alkenes into thianthrene-derived cationic electrophiles. These linchpin intermediates generated selectively and undergo diverse array mechanistically distinct with abundant nucleophiles. Taken together, this unlocks suite net oxidative transformations been elusive using conventional strategies. This Minireview describes these is organized around three synthons formally accessible from via thianthrenation: 1) alkenyl cations; 2) vicinal dications; 3) allyl cations. Throughout Minireview, we illustrate how thianthrenium salts address key limitations endemic to classic alkene-derived electrophiles highlight mechanistic origins distinctions wherever possible.

Language: Английский

Citations

10