Ph3P/ICH2CH2I-promoted reductive deoxygenation of alcohols DOI

Wen-Huan Tang,

Xing Zheng,

Xu Yao

et al.

Organic & Biomolecular Chemistry, Journal Year: 2023, Volume and Issue: 21(45), P. 8989 - 8992

Published: Jan. 1, 2023

Owing to the ubiquity of hydroxyl group, reductive deoxygenation alcohols has become an active research area. The classic Barton-McCombie reaction suffers from a tedious two-step procedure. New efficient methods have been developed, but they some limitations, such as narrow substrate scope and use moisture-sensitive Lewis acids. In this work, we describe Ph3P/ICH2CH2I-promoted with NaBH4. process is applicable benzyl, allyl propargyl alcohols, also primary secondary demonstrating wide good level functional group tolerance. This protocol features convenient operation low cost all reagents.

Language: Английский

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
Direct Deoxygenation of Free Alcohols and Ketones DOI Creative Commons
Haoyu Zhang, Guansheng Ma, Hanbo Chen

et al.

JACS Au, Journal Year: 2025, Volume and Issue: unknown

Published: April 11, 2025

This work presents a feasible method for the elimination of alcohol hydroxyls through direct activation typical alkyl alcohols using neutral boron radicals. transformation necessitates proficient reagent capable swiftly activating hydroxyl group to produce radicals, thereby circumventing numerous alternative side reactions associated with group. To implement this method, we have created an innovative photocatalytic reaction system that oxidizes sodium tetraphenylboron which subsequently enable homolytic conversion groups. deoxygenation technique no additional preactivation and yields favorable outcomes majority substrates. The facilitates methylene reduction aldehydes ketones. Mechanistic studies established likely initiates production alcohols, thereafter undergoing dehydroxylation yield methylene-reduced products.

Language: Английский

Citations

0
Photoinduced transition-metal and external photosensitizer free cross-coupling of aryl triflates with trialkyl phosphites DOI
Qian Dou, Geng Li, Bin Cheng

et al.

Chemical Communications, Journal Year: 2021, Volume and Issue: 57(68), P. 8429 - 8432

Published: Jan. 1, 2021

Photoinduced phosphonation of aryl triflates with trialkyl phosphites via a tandem single-electron-transfer, C–O bond cleavage and Arbuzov rearrangement process in the absence transition-metal external photosensitizer is reported.

Language: Английский

Citations

21
Light-driven transition-metal-free direct decarbonylation of unstrained diaryl ketones via a dual C–C bond cleavage DOI Creative Commons
Dawei Cao, Mohamad Ataya, Zhangpei Chen

et al.

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: April 4, 2022

The cleavage and formation of carbon-carbon bonds have emerged as powerful tools for structural modifications in organic synthesis. Although transition-metal-catalyzed decarbonylation unstrained diaryl ketones provides a viable protocol to construct biaryl structures, the use expensive catalyst high temperature (>140 oC) greatly limited their universal applicability. Moreover, direct activation two inert C - without assistance metal has been great challenge due inherent stability (nonpolar, thermo-dynamically stable, kinetically inert). Here we report an efficient light-driven transition-metal-free strategy compounds through dual cleavage. This reaction featured mild conditions, easy-to-handle reactants reagents, excellent functional groups tolerance. mechanistic investigation DFT calculation suggest that this proceeds dioxy radical intermediate via single-electron-transfer (SET) process between photo-excited ketone DBU mediated by DMSO, followed removal CO2 compounds.

Language: Английский

Citations

15
Visible-light induced transition-metal and photosensitizer-free conversion of aldehydes to acyl fluorides under mild conditions DOI Creative Commons

Yatao Lang,

Xinlong Han,

Xiangjun Peng

et al.

Green Synthesis and Catalysis, Journal Year: 2022, Volume and Issue: 3(4), P. 373 - 376

Published: April 30, 2022

Acyl fluorides are powerful synthons for acylation with wide application in the synthesis of valued compounds, especially peptides. Herein, a practical and catalyst-free method acyl from aldehydes via C(sp2)–H fluorination is reported. This enables conversion both aliphatic aromatic into good to excellent yields by visible-light under mild conditions absence transition-metal external photosensitizer. A variety functional groups were well tolerated this transformation. green provides pathway synthesize conditions.

Language: Английский

Citations

15
Light-driven MPV-type reduction of aryl ketones/aldehydes to alcohols with isopropanol under mild conditions DOI
Dawei Cao, Shumei Xia, Pan Pan

et al.

Green Chemistry, Journal Year: 2021, Volume and Issue: 23(19), P. 7539 - 7543

Published: Jan. 1, 2021

A light-driven photocatalyst-free strategy for reducing ketones/aldehydes to alcohols using isopropanol as the agent and solvent in presence of t BuOLi under mild conditions is developed.

Language: Английский

Citations

17
Visible-light-induced transition metal and photosensitizer free decarbonylative addition of amino-arylaldehydes to ketones DOI Creative Commons
Yi Wang,

Yatao Lang,

Chao‐Jun Li

et al.

Chemical Science, Journal Year: 2021, Volume and Issue: 13(3), P. 698 - 703

Published: Dec. 21, 2021

The decarbonylative-coupling reaction is generally promoted by transition metals (via organometallic complexes) or peroxides radical intermediates), often at high temperatures to facilitate the CO release. Herein, a visible-light-induced, metal and external photosensitizer free decarbonylative addition of benzaldehydes ketones/aldehydes room temperature reported. Tertiary/secondary alcohols were obtained in moderate excellent yields using CsF under mild conditions. detailed mechanistic investigation showed that proceeded through photoexcitation-decarbonylation aldehyde generate an aromatic anion, followed its ketones/aldehydes. mechanism was verified density functional theory (DFT) calculations.

Language: Английский

Citations

15
Conformational Flexibility as a Tool for Enabling Site-Selective Functionalization of Unactivated sp3 C–O Bonds in Cyclic Acetals DOI Creative Commons
Ciro Romano, Laura Talavera, Enrique Gómez‐Bengoa

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(26), P. 11558 - 11563

Published: June 24, 2022

A dual catalytic manifold that enables site-selective functionalization of unactivated sp3 C–O bonds in cyclic acetals with aryl and alkyl halides is reported. The reaction triggered by an appropriate σ*–p orbital overlap prior to cleavage, thus highlighting the importance conformational flexibility both reactivity site selectivity. protocol characterized its excellent chemoselectivity profile, offering new vistas for activating strong σ linkages.

Language: Английский

Citations

11
Recent Progress in Light-Driven Direct Dehydroxylation and Derivation of Alcohols DOI Open Access

Boyu Yan,

Jieliang Wu,

Jinfei Deng

et al.

Chinese Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 43(9), P. 3055 - 3055

Published: Jan. 1, 2023

Conventional methods for the reduction of alcohols mainly deal with indirect cleavages Csp3-O bond involving tedious activated steps.In contrast, more straightforward direct naturally abundant aliphatic to alkanes or other reductive derivatives poses a challenge organic chemists due inherently stable and less reactive bond.The development strategies induced by light is utmost importance their atom economy, step economy redox many progresses have been made in this area these years.However, very few reviews on topic has reported so far.Herein, recent progress light-driven deoxygenation emphasis important advances last ten years reviewed, which expected further promote vigorous field.

Language: Английский

Citations

5
Nickel-Catalyzed Stereoselective Alkenylation of Ketones Mediated by Hydrazine DOI Creative Commons
Shumei Xia, Dawei Cao, Huiying Zeng

et al.

JACS Au, Journal Year: 2022, Volume and Issue: 2(8), P. 1929 - 1934

Published: July 25, 2022

The direct conversion of naturally abundant carbonyl compounds provides a powerful platform for the efficient synthesis valuable chemicals. In particular, ketones to alkenes is commonly encountered chemical transformation, often achieved via multistep Shapiro reaction with tosylhydrazone and over stoichiometric organolithium or Grignard reagent. Herein, we report an earth nickel-catalyzed alkenylation methylene afford wide range alkene derivatives, mediated by hydrazine. protocol features broad substrate scope (including alkyl ketones, aryl aldehydes), good functional group compatibility, mild conditions, water tolerance, only environmentally friendly N2, H2, H2O as theoretical byproducts. Moreover, gram-scale yield generation pharmaceutical intermediates highlighted its practical applicability.

Language: Английский

Citations

9