Zn(II)-Stabilized Azo-Anion Radical-Catalyzed Dehydrogenative Synthesis of Olefins DOI
Subhasree Pal, Amit Kumar Guin,

Subhankar Khanra

et al.

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

Published: Dec. 16, 2024

Herein, we describe a Zn-catalyzed atom-economical, inexpensive, and sustainable method for preparing broad spectrum of substituted olefins utilizing alcohols as the main precursor. Using Zn(II) complex [ZnLCl2] (1) redox-noninnocent ligand 2-((4-chlorophenyl)diazenyl)-1,10-phenanthroline (L), various (E)-olefins were prepared in good yields by coupling with sulfones aryl cyanides under an inert atmosphere. Under aerial atmosphere, vinyl nitriles isolated up to 82% yield reacting benzyl presence 1. Control experiments mechanistic investigation indicate active involvement aryl-azo electron hydrogen reservoir, permitting 1 perform promising catalyst.

Language: Английский

Ruthenium‐Catalyzed α‐Alkylation of Arylacetonitriles with Primary Alcohols: N‐heterocyclic Carbene‐Amine's Promotional Influence DOI

Xurui Wei,

Xiuju Cai,

Ming Huang

et al.

ChemistrySelect, Journal Year: 2025, Volume and Issue: 10(7)

Published: Feb. 1, 2025

Abstract Transition‐metal‐catalyzed α‐alkylation of nitriles with alcohols is an environmentally benign reaction, and the development simple efficient catalysts for this transformation a growing area research. In study, we report serial bidentate N ‐heterocyclic carbene (NHC) ruthenium complexes different extra donors alcohols. Through adjusting backbone NHC ligands, catalytic activities these could be controlled. The complex ( Ru3 ) bearing amine donor benzimidazolium exhibited highest activity. A large variety α‐alkylated were obtained in 30%–88% yields, by using 1 mol% amount Cs 2 CO 3 (20 mol%). Detailed control experiments deuterium‐labeling suggested that reaction proceeds via borrowing hydrogen pathway.

Language: Английский

Citations

0
Heterogeneous Mn@CeO2 Catalyst for α-Alkylation of Ketones with Alcohols via Hydrogen-Borrowing Strategy DOI Creative Commons

Rajagopal Swaathy,

S. Karthikeyan

ACS Omega, Journal Year: 2025, Volume and Issue: 10(9), P. 9649 - 9660

Published: Feb. 24, 2025

Construction of a C-C bond via alkylation ketones with alcohol as the alkylating source by employing hydrogen-borrowing strategy is attracting significant attention and highly appealing due to its simplicity, cost-effectiveness, environmental benefits, fact that water only byproduct. The development heterogeneous catalysts based on nonprecious base metals progressing rapidly. Our newly disclosed manganese-doped cerium oxide nanocomposite (10 wt % Mn@CeO2) stands out cost-efficient air-stable catalyst, synthesized through straightforward coprecipitation method employed for α-alkylation primary alcohols strategy. X-ray diffraction (XRD) analysis confirms high crystallinity CeO2, while field emission scanning electron microscopy (FE-SEM) high-resolution transmission (HR-TEM) images reveal MnO2 nanoparticles, measuring 19 nm in size, uniformly decorated rod-shaped CeO2 which have size 33 nm. photoelectron spectroscopy (XPS) uncovers presence Mn4+ species embedded nanorods. Electron paramagnetic resonance (EPR) further indicates surface defects contribute impressive catalytic yield, ranges from 70 98% α-alkylated ketones. Thermogravimetric (TGA) demonstrates remarkable thermal stability maintaining up 800 °C. Additionally, inductively coupled plasma mass spectrometry (ICP-MS) no leaching Mn ions, emphasizing heterogeneity catalyst. Remarkably, 10 Mn@CeO2 recycled six cycles loss activity. This study underscores synergistic effect between metal redox pair key exceptional activity reactions, making promising catalyst sustainable efficient formation.

Language: Английский

Citations

0
Organic Peroxides in Transition-Metal-Free Cyclization and Coupling Reactions (C–C) via Oxidative Transformation DOI Creative Commons
Amin Rezaeifard, Fatemeh Doraghi, Fatemeh Akbari

et al.

ACS Omega, Journal Year: 2025, Volume and Issue: unknown

Published: April 14, 2025

Transition-metal-free transformations are recognized as green and sustainable methods for constructing carbon-carbon bonds in organic synthesis. This review describes the application of six peroxides, including tert-butyl hydroperoxide (TBHP), di-tert-butyl peroxide (DTBP), peroxybenzoate (TBPB), benzoyl (BPO), dialauroyl (DLP), diguyl (DCP), C-C bond construction, highlighting selected examples mechanisms challenging transformations. Each section concludes with a detailed overview suitable reagents various coupling reactions strengths weaknesses reported works. work aims to inspire further innovations transition-metal-free oxidative transformations, promoting eco-friendly chemical processes paving way new peroxide-based synthesis methods.

Language: Английский

Citations

0
Zn(II)-Stabilized Azo-Anion Radical-Catalyzed Dehydrogenative Synthesis of Olefins DOI
Subhasree Pal, Amit Kumar Guin,

Subhankar Khanra

et al.

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

Published: Dec. 16, 2024

Herein, we describe a Zn-catalyzed atom-economical, inexpensive, and sustainable method for preparing broad spectrum of substituted olefins utilizing alcohols as the main precursor. Using Zn(II) complex [ZnLCl2] (1) redox-noninnocent ligand 2-((4-chlorophenyl)diazenyl)-1,10-phenanthroline (L), various (E)-olefins were prepared in good yields by coupling with sulfones aryl cyanides under an inert atmosphere. Under aerial atmosphere, vinyl nitriles isolated up to 82% yield reacting benzyl presence 1. Control experiments mechanistic investigation indicate active involvement aryl-azo electron hydrogen reservoir, permitting 1 perform promising catalyst.

Language: Английский

Citations

0