Search results for "Catalysis"

Cyclic ureas (DMI, DMPU) as efficient, sustainable ligands in iron-catalyzed C(sp2)–C(sp3) coupling of aryl chlorides and tosylates

2017

Iron-catalyzed cross-coupling has emerged as a powerful tool for sustainable catalysis. However, by far the most common ligand in iron-catalyzed cross-couplings for preparative and industrial applications is reprotoxic NMP. Herein, we report that cyclic ureas (DMI, DMPU) are efficient and sustainable alternatives to NMP in iron-catalyzed alkylations of aryl chlorides and tosylates with alkyl Grignard reagents. This environmentally benign method accomplishes traditionally challenging C(sp2)–C(sp3) cross-coupling with organometallics possessing β-hydrogens with efficiency matching or superseding NMP. The reaction is compatible with a variety of electrophilic functional handles. Applications t…

Cyclic dipeptides: catalyst/promoter-free, rapid and environmentally benign cyclization of free amino acids

2011

“The best catalyst is no catalyst.” With growing public concern over global warming and the amount of greenhouse gases, it is important to reduce the amount of chemicals and eliminate waste, to obtain better results in a simple, selective, safe, and environmentally benign fashion compared to conventional tedious chemical synthesis. Herein, we disclose an environmentally benign, rapid, catalyst/promoter/coupling reagent-free cyclization procedure of free amino acids to furnish exclusively cyclic dipeptides (2,5-diketopiperazines, DKPs) in excellent or even quantitative yield, along with their solid state self-assembling properties. This process is extremely simple and highly efficient with l…

Sustainable and cost-efficient electro-synthesis of formamidine acetate from cyanamide in aqueous acidic electrolyte

2021

Formamidine represents a versatile building block in synthetic organic chemistry. We developed a new electrochemical synthesis of formamidine acetate by cathodic reduction of cyanamide in an aqueous electrolyte and in high yield. The crude product could be used for further conversions, such as to pyrimidines without purification. Compared to established synthetic routes neither prior processing of cyanamide was necessary, nor precious transition-metal catalyst were required, nor any reagent waste was produced, and only biocompatible and sustainable solvents were employed for this process, following the requirements of green chemistry.

Photocatalytic Partial Oxidation of 5‐Hydroxymethylfurfural (HMF) to 2,5‐Diformylfuran (DFF) Over a Covalent Triazine Framework in Water

2020

Dehydrogenative Anodic Cyanation Reaction of Phenols in Benzylic Positions

2019

Evaluation of Antiradical Activity and Reducing Capacity of Synthesised Bispyridinium Dibromides Obtained by Quaternisation of 4-Pyridyl-1,4-dihydrop…

2015

New bispyridinium dibromides based on the 1,4-dihydropyridine (1,4-DHP) cycle were synthesised in the reaction between 4-pyridyl-1,4-DHP derivatives and propargyl bromide. It has been shown that variation of the substituent position on the pyridine as well as small changes in the electronic nature of the 1,4-DHP cycle as a result of the substituent nature at the 3 and 5 positions do not affect the course of the reaction and in all cases the corresponding bispyridinium dibromides 4a–e were formed. The antiradical activity, using 1,1-diphenyl-2-picrylhydrazine as a free radical scavenger, and the reducing capacity using phosphomolybdenum complexes have been evaluated for the newly synthesise…

Frontispiece: A Novel Cathode Material for Cathodic Dehalogenation of 1,1‐Dibromo Cyclopropane Derivatives

2015

Metal‐Free Twofold Electrochemical C−H Amination of Activated Arenes: Application to Medicinally Relevant Precursor Synthesis

2020

Abstract The efficient production of many medicinally or synthetically important starting materials suffers from wasteful or toxic precursors for the synthesis. In particular, the aromatic non‐protected primary amine function represents a versatile synthetic precursor, but its synthesis typically requires toxic oxidizing agents and transition metal catalysts. The twofold electrochemical amination of activated benzene derivatives via Zincke intermediates provides an alternative sustainable strategy for the formation of new C−N bonds of high synthetic value. As a proof of concept, we use our approach to generate a benzoxazinone scaffold that gained attention as a starting structure against ca…

Palladium Supported on Cross-Linked Imidazolium Network on Silica as Highly Sustainable Catalysts for the Suzuki Reaction under Flow Conditions

2013

Highly cross-linked imidazolium-based materials, obtained by radical oligomerization of bis-vinylimidazolium salts in the presence of 3-mercaptopropyl-modified silica gel, were used as supports for palladium catalysts. Thanks to the high imidazolium loading these materials were able to support a high amount of the metal (10 wt%). Such materials were characterized by several techniques (13C magic angle spinning nuclear magnetic resonance, the Brunauer-Emmett-Teller technique, X-ray photoelectron spectroscopy, and transmission electron microscopy). The palladium catalysts displayed good activity allowing the synthesis of several biphenyl compounds in high yields working with only 0.1 mol% of …

An E-Factor Minimized Protocol for a Sustainable and Efficient Heck Reaction in Flow

2014

A highly sustainable and waste-minimized protocol for Heck coupling has been defined. Optimal conditions have been defined by exploiting a heterogeneous catalyst based on supported ionic liquid-like phases featuring high Pd loading (10 wt %) and by optimizing its efficiency in a recoverable green reaction medium (acetonitrile/water azeotrope). Pure products 4a–l and 6a–h have been isolated chromatography-free in high yields (74–99%) and with extremely low environmental factor (E-factor) values (2.3–5.0). With the application of flow technology, the selected heterogeneous base and Pd catalyst have been fully recovered and reused, and minimum palladium leaching allowed for isolation of the fi…