27070-05-9

Upstream product

• 623-73-4 diazoacetic acid ethyl ester 
• 98-83-9 isopropenylbenzene 
• 1073-67-2 4-vinylbenzyl chloride 
• 637-50-3 1-phenylpropene 

Relevant academic research and scientific papers

Synthesis, Characterization and Biological and Catalytic Activities of Propionitril: Ligated Transition Metal Complexes with [B(C6F5)4] as Counter Anion

Abstract: A series of new metal complexes of the general formula [M (NCCH2CH3)6] [B (C6F5)4]2, where M: Cu, Fe, Co, Ni, Zn, Mn, have been synthesized. Resulting complexes have be

Iron Lewis acid catalyzed reactions of ethyldiazoacetate with styrene and α-methylstyrene: Formation of cyclopropanes with Cis selectivity

The iron Lewis acid, (η5-C5H5)Fe+(CO)2(THF)BF(4-) catalyzes the reaction of ethyldiazoacetate with styrene and α-methylstyrene to provide cyclopropanes with a preference for the cis isomer.

Stabilization and recovery of gold catalysts in the cyclopropanation of alkenes within ionic liquids

Au(I) and Au(III) salts (NaAuCl4 and KAuCN2 respectively) were found to be active catalysts for the cyclopropanation of alkenes with ethyldiazoacetate, in many cases affording high yields of cyclopropanecarboxylates. But these gold s

Cyclopropanation reactions catalysed by copper(II)-exchanged clays and zeolites. Influence of the catalyst on the selectivity

The reaction of ethyl diazoacetate with styrene is catalysed by CuII-exchanged clays and zeolites; the trans/cis selectivity strongly depends on the nature of the catalyst and when using CuII-K10 montmorillonite the normal selectivit

Selective carbene transfer to amines and olefins catalyzed by ruthenium phthalocyanine complexes with donor substituents

Electron-rich ruthenium phthalocyanine complexes were evaluated in carbene transfer reactions from ethyl diazoacetate (EDA) to aromatic and aliphatic olefins as well as to a wide range of aromatic, heterocyclic and aliphatic amines for the first time. It was revealed that the ruthenium octabutoxyphthalocyanine carbonyl complex [(BuO)8Pc]Ru(CO) is the most efficient catalyst converting electron-rich and electron-poor aromatic olefins to cyclopropane derivatives with high yields (typically 80-100%) and high TON (up to 1000) under low catalyst loading and nearly equimolar substrate/EDA ratio. This catalyst shows a rare efficiency in the carbene insertion into amine N-H bonds. Using a 0.05 mol% catalyst loading, a high amine concentration (1 M) and 1.1 eq. of EDA, a number of structurally divergent amines were selectively converted to mono-substituted glycine derivatives with up to quantitative yields and turnover numbers reaching 2000. High selectivity, large substrate scope, low catalyst loading and practical reaction conditions place [(BuO)8Pc]Ru(CO) among the most efficient catalysts for the carbene insertion into amines.

Comparative Study of the Electronic Structures of μ-Oxo, μ-Nitrido, and μ-Carbido Diiron Octapropylporphyrazine Complexes and Their Catalytic Activity in Cyclopropanation of Olefins

The electronic structure of three single-Atom bridged diiron octapropylporphyrazine complexes (FePzPr8)2X having Fe(III)-O-Fe(III), Fe(III)-N-Fe(IV) and Fe(IV)-C-Fe(IV) structural units was investigated by M?ssbauer spectroscopy and density functional theory (DFT) calculations. In this series, the isomer shift values decrease, whereas the values of quadrupole splitting become progressively greater indicating the increase of covalency of Fe-X bond in the μ-oxo, μ-nitrido, μ-carbido row. The M?ssbauer data point to low-spin systems for the three complexes, and calculated data with B3LYP-D3 show a singlet state for μ-oxo and μ-carbido and a doublet state for μ-nitrido complexes. An excellent agreement was obtained between B3LYP-D3 optimized geometries and X-ray structural data. Among (FePzPr8)2X complexes, μ-oxo diiron species showed a higher reactivity in the cyclopropanation of styrene by ethyl diazoacetate to afford a 95% product yield with 0.1 mol % catalyst loading. A detailed DFT study allowed to get insight into electronic structure of binuclear carbene species and to confirm their involvement into carbene transfer reactions.

Iron/N-doped graphene nano-structured catalysts for general cyclopropanation of olefins

The first examples of heterogeneous Fe-catalysed cyclopropanation reactions are presented. Pyrolysis of in situ-generated iron/phenanthroline complexes in the presence of a carbonaceous material leads to specific supported nanosized iron particles, which are effective catalysts for carbene transfer reactions. Using olefins as substrates, cyclopropanes are obtained in high yields and moderate diastereoselectivities. The developed protocol is scalable and the activity of the recycled catalyst after deactivation can be effectively restored using an oxidative reactivation protocol under mild conditions. This journal is

Iron and Ruthenium Glycoporphyrins: Active Catalysts for the Synthesis of Cyclopropanes and Aziridines

In view of the relevance of cyclopropanes and aziridines as synthetic building blocks as well as active parts in biological and pharmaceutical compounds, the development of sustainable synthetic procedures for obtaining these products continues to be a si

Chemoselective Cyclopropanation over Carbene Y-H Insertion Catalyzed by an Engineered Carbene Transferase

Hemoproteins have recently emerged as promising biocatalysts for promoting a variety of carbene transfer reactions including cyclopropanation and Y-H insertion (Y = N, S, Si, B). For these and synthetic carbene transfer catalysts alike, achieving high chemoselectivity toward cyclopropanation in olefin substrates bearing unprotected Y-H groups has proven remarkably challenging due to competition from the more facile carbene Y-H insertion reaction. In this report, we describe the development of a novel artificial metalloenzyme based on an engineered myoglobin incorporating a serine-ligated Co-porphyrin cofactor that is capable of offering high selectivity toward olefin cyclopropanation over N-H and Si-H insertion. Intramolecular competition experiments revealed a distinct and dramatically altered chemoselectivity of the Mb(H64V,V68A,H93S)[Co(ppIX)] variant in carbene transfer reactions compared to myoglobin-based variants containing the native histidine-ligated heme cofactor or other metal/proximal ligand substitutions. These studies highlight the functional plasticity of myoglobin as a "carbene transferase" and illustrate how modulation of the cofactor environment within this metalloprotein scaffold represents a valuable strategy for accessing carbene transfer reactivity not exhibited by naturally occurring hemoproteins or transition metal catalysts.

ARTIFICIAL METALLOENZYMES CONTAINING NOBLE METAL-PORPHYRINS

The present invention is drawn to artificial metalloenzymes for use in cyclopropanation reactions, amination and C—H insertion.