eEtherification: An Electrochemical Strategy toward the Synthesis of Sterically Hindered Dialkyl Ethers from Activated Alcohols DOI
Cyrille Kiaku, Simon Kaltenberger, Daniel Raydan

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 17, 2024

Traditional etherification methods, although staples in synthetic chemistry, often fall short the efficient construction of sterically hindered dialkyl ethers, especially under mild and practical conditions. Recent advances have attempted to address these limitations, typically relying on transition metal catalysts, external reductants, or harsh reaction In this work, we disclose a novel electrochemical approach that enables synthesis ethers from economically relevant readily accessible alcohols without need for sacrificial oxidants. Our protocol exploits conditions generate reactive carbocations, which are subsequently captured by alcohol nucleophiles yield desired ethers. This method is cost-effective, practical, broad scope, providing valuable addition chemists' toolkit ether synthesis.

Language: Английский

Triflic Acid‐Catalyzed Dehydrative Amination of 2‐Arylethanols with Weak N‐Nucleophiles in Hexafluoroisopropanol DOI Creative Commons
Max Van Hoof, Robert J. Mayer, Joseph Moran

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 21, 2024

Abstract The catalytic deoxyamination of readily available 2‐arylethanols offers an appealing, simple, and straightforward means accessing β‐(hetero)arylethylamines biological interest. Yet, it currently represents a great challenge to synthetic chemistry. In most cases, the alcohol has be either pre‐activated in situ or converted into reactive carbonyl intermediate, limiting substrate scope for some methods. Examples direct dehydrative amination are thus still scarce. Here, we describe protocol based on synergy triflic acid hexafluoroisopropanol, which enables stereospecific broad array 2‐arylethanols, does not require any pre‐activation alcohol. This approach yields high value‐added products incorporating sulfonamide, amide, urea, aniline functionalities. addition, this was applied sulfidation 2‐arylethanols. Mechanistic experiments DFT computations indicate formation phenonium ions as key intermediates reaction.

Language: Английский

Citations

5
Visible-light-induced radical-cascade alkylation/cyclization of acrylamides: Access to 3,3-dialkylated oxindoles DOI
Pengyuan Yang, Lili Wang, Yan Meng

et al.

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

Published: Jan. 1, 2025

A visible-light-induced deoxygenative alkylation/cyclization of acrylamides with alcohols activated by CS 2 has been developed using xanthate salts as alkyl radical precursors in the presence tricyclohexylphosphine.

Language: Английский

Citations

0
Photocatalytic Redox-Neutral and Reductive Deoxygenative Alkylation of Benzyl Alcohols Using N-Acyl Carbamothioates as Radical Precursors DOI
Junhao Li, Yuanxin Liu, Li Wang

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 26, 2025

Herein, we report a photocatalytic redox-neutral and reductive deoxygenative alkylation of N-acyl carbamothioates from benzylic alcohols, with substituted Hantzsch esters allylic sulfones to afford unsymmetrical 1,2-diaryl ethanes allylarylmethanes, respectively. This protocol facilitates facile deoxyalkylation primary, secondary, tertiary alcohol-derived carbamothioates, which features mild reaction conditions, broad functional group tolerance, the obviation external S/O trapping reagents as well transition metal-coupling catalysts.

Language: Английский

Citations

0
A Sterically Tuned 2-Fluoropyridinium Salt for the Catalyst-Free, Visible-Light-Mediated Deoxygenation of Alcohols via an Electron Donor–Acceptor Complex DOI
Takeshi Nanjo, Yixuan Lin, Yuki Fujii

et al.

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

Published: March 7, 2025

We here report the use of a sterically tuned 2-fluoro-1-methylpyridinium salt for catalyst-free, visible-light-mediated deoxygenative transformation alcohols through alkoxypyridinium intermediates. The key to this process is introduction bulky cyclohexyl group at 3-position pyridinium ring, which enforces favorable conformation C-O bond cleavage and formation an electron donor-acceptor complex between ring amines.

Language: Английский

Citations

0
Deuteriodifluoromethyl Sulfonium Ylides: Easily Accessible Reagents for Electrophilic Deuteriodifluoromethylation of O-Nucleophiles DOI
Wenting Liu,

Huilin Lan,

Heping Xia

et al.

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

Published: March 25, 2025

A class of sulfonium ylide-based reagents for electrophilic deuteriodifluoromethylation is reported. Thus, a wide array ubiquitous O-nucleophiles such as sulfonic acid, alcohol, carboxyl and phosphoric acid are deuteriodifluoromethylated, providing straightforward approach to access the OCF2D-functionalizazed scaffolds that otherwise challenging synthesize using conventional methods. This base-free protocol also displays broad functional group compatibility amenable effective late-stage modification bioactive molecules.

Language: Английский

Citations

0
Photocatalytic Amine-Promoted Selective Hydrochlorination and sp3 C–O Acylation of Alkyne-Tethered Methyl Ethers with Aldehydes DOI

Liping Huo,

Shengqing Zhu,

Yaheng Zhao

et al.

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

Published: March 27, 2025

We present a photoredox and alkylamine-assisted approach for the selective hydrochlorination acylation of sp3 C–O bonds in alkynyl methyl ethers using aldehydes. This method leverages cascade radical processes─including chlorine addition, hydrogen atom transfer, situ imine spin-center shift─to enable alkynes spontaneous cleavage bonds. The transformation accommodates broad range internal alkyne-tethered aldehydes, providing an efficient streamlined pathway to chloro-alkenyl ketones. Utilizing only photocatalyst, chloride, propylamine under light irradiation, this strategy offers practical complementary alternative previous protocols.

Language: Английский

Citations

0
Bench-Stable Cerium(IV) Benzoate: A Versatile LMCT Catalyst for Selective Dehydroxymethylative Functionalization DOI
Hanwen Liang, Long‐Li Lai, Kaining Zhang

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 8069 - 8077

Published: April 30, 2025

Language: Английский

Citations

0
Dehomologative C–C Borylation of Aldehydes and Alcohols via a Rh-Catalyzed Dehydroformylation–Borylation Relay DOI Creative Commons
Kuhali Das, Nikodem Kuźnik, Paweł Dydio

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: May 12, 2025

The dehomologative conversion of linear or α-methyl aldehydes to vinyl boronates is achieved via a one-pot sequence rhodium-catalyzed transfer dehydroformylation and borylation the resulting alkenes. Similarly, allylic aliphatic alcohols are converted through involving, respectively, isomerization dehydrogenation aldehyde intermediates, followed by dehydroformylation-borylation. can be further hydrogenated alkyl using same rhodium precatalyst, enabling all five catalytic steps with single catalyst system.

Language: Английский

Citations

0
Recent Advances in the Synthesis of Cyclic Sulfone Compounds with Potential Biological Activity DOI Creative Commons
Hong‐Li Huang,

Ya-Qian Shi,

J. H. Ning

et al.

Molecules, Journal Year: 2024, Volume and Issue: 29(24), P. 5868 - 5868

Published: Dec. 12, 2024

In recent years, cyclic sulfone compounds, a subset of biologically active heterocyclic have gained considerable attention due to their potential in the development novel pharmaceutical ingredients. This review focuses on identifying simple, mild, environmentally friendly, and efficient synthesis methods. Various catalytic approaches for compounds are systematically reviewed, highlighting advantages applications development.

Language: Английский

Citations

1
eEtherification: An Electrochemical Strategy toward the Synthesis of Sterically Hindered Dialkyl Ethers from Activated Alcohols DOI
Cyrille Kiaku, Simon Kaltenberger, Daniel Raydan

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 17, 2024

Traditional etherification methods, although staples in synthetic chemistry, often fall short the efficient construction of sterically hindered dialkyl ethers, especially under mild and practical conditions. Recent advances have attempted to address these limitations, typically relying on transition metal catalysts, external reductants, or harsh reaction In this work, we disclose a novel electrochemical approach that enables synthesis ethers from economically relevant readily accessible alcohols without need for sacrificial oxidants. Our protocol exploits conditions generate reactive carbocations, which are subsequently captured by alcohol nucleophiles yield desired ethers. This method is cost-effective, practical, broad scope, providing valuable addition chemists' toolkit ether synthesis.

Language: Английский

Citations

0