4103-57-5

Upstream product

• 623-73-4 diazoacetic acid ethyl ester 
• 1073-67-2 4-vinylbenzyl chloride 
• 106-39-8 bromochlorobenzene 
• 91496-20-7 ethyl 2-(phenylsulfanyl)cyclopropane-1-carboxylate 
• 1099-45-2 ethyl (triphenylphosphoranylidene)acetate 
• 24393-52-0 ethyl (E)-3-(4-chlorophenyl)prop-2-enoate 
• 1774-47-6 trimethylsulfoxonium iodide 
• 104-88-1 4-chlorobenzaldehyde 
• 186581-53-3 diazomethane 
• 18410-18-9 γ-(4-chlorophenyl)-γ-butyrolactone 
• 14593-46-5 sodium tert-pentoxide 
• 100117-11-1 4-Chlor-4-(4-chlor-phenyl)-buttersaeureethylester 
• 3984-34-7 4-(4-chlorophenyl)-4-oxobutanoic acid 

Downstream Products

• 4157-47-5 (±)-trans-2-(4-chlorophenyl)cyclopropane-1-carboxylic acid 
• 132145-63-2 trans-2-(4-chlorophenyl)cyclopropane-1-carbaldehyde 
• 1278662-50-2 (trans-2-(4-chlorophenyl)cyclopropyl)methanol 
• 90794-53-9 trans-2-(4-Chlor-phenyl)-cyclopropan-carbonsaeure-⁽¹⁾-hydrazid 
• 61114-41-8 (±)-trans-2-(4-chlorophenyl)cyclopropan-1-amine 
• 72228-99-0 methyl trans-2-(p-chlorophenyl)cyclopropanecarboxylate 

Relevant academic research and scientific papers

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.

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

Metal-free domino Cloke-Wilson rearrangement-hydration-dimerization of cyclopropane carbaldehydes: A facile access to oxybis(2-aryltetrahydrofuran) derivatives

In this work, we have demonstrated a metal-free transformation of cyclopropane carbaldehydes to oxybis(2-aryltetrahydrofuran) derivatives via a domino Cloke-Wilson rearrangement-hydration-dimerization sequence. Commercially inexpensive p-toluene sulfonic acid (PTSA) was used as a Br?nsted acid catalyst, and reactions were conducted in an open-flask. Detection of reaction intermediates were carried to get an insight into the reaction pathway.

Regioselective Br?nsted Acid-Catalyzed Annulation of Cyclopropane Aldehydes with N′-Aryl Anthranil Hydrazides: Domino Construction of Tetrahydropyrrolo[1,2- a]quinazolin-5(1 H)ones

A highly regioselective synthesis of tetrahydropyrrolo[1,2-a]quinazolin-5(1H)one derivatives was achieved by reacting cyclopropane aldehydes with N′-aryl anthranil hydrazides in the presence of p-toluene sulfonic acid (PTSA). The transformation involves domino imine formation and intramolecular cyclization to form 2-arylcyclopropyl-2,3-dihydroquinolin-4(1H)-one, followed by nucleophilic ring opening of the cyclopropyl ring to form desired tetrahydropyrrolo[1,2-a]quinazolin-5(1H)one in good to excellent yield with complete regioselectivity. This protocol tolerates a great variety of functional groups and thus provides a simple and step-efficient method for pyrroloquinazolinone synthesis.

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

Synthesis of Photosensitive Cyclopropane-Containing Polymers

New cyclopropyl methacrylate monomers were prepared, their radical polymerization was performed, and the composition and structure of the polymers obtained, containing reactive UV-sensitive fragments, were determined. Experiments on photochemical cross-li

Metal-Free Ring Opening Cyclization of Cyclopropane Carbaldehydes and N-Benzyl Anilines: An Eco-Friendly Access to Functionalized Benzo[b]azepine Derivatives

Herein, we report a p-toluenesulfonic acid (PTSA) initiated mild and user-friendly ring opening/domino ring opening cyclization reaction (depends on substituent present in N-benzyl aniline) of cyclopropane carbaldehyde and N-benzyl aniline towards the formation of substituted 4-amino butanal/2,3-dihydro-1H-benzo[b]azepine. The product dihydro-1H-benzo[b]azepine was also converted into the corresponding tetrahydro-1H-benzo[b]azepine. (Figure presented.).

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.

An Artificial Heme Enzyme for Cyclopropanation Reactions

An artificial heme enzyme was created through self-assembly from hemin and the lactococcal multidrug resistance regulator (LmrR). The crystal structure shows the heme bound inside the hydrophobic pore of the protein, where it appears inaccessible for substrates. However, good catalytic activity and moderate enantioselectivity was observed in an abiological cyclopropanation reaction. We propose that the dynamic nature of the structure of the LmrR protein is key to the observed activity. This was supported by molecular dynamics simulations, which showed transient formation of opened conformations that allow the binding of substrates and the formation of pre-catalytic structures.

Cyclopropanation of alkenes with metallocarbenes generated from monocarbonyl iodonium ylides

Reacting Wittig reagents and the hypervalent iodine reagent iodosotoluene, in the presence of 10 mol% Cu(tfacac)2 and 5 equiv. of alkene, results in a novel cyclopropanation reaction. The reagent combination is believed to generate a transient monocarbonyl iodonium ylide (MCIY) in situ, which can be intercepted by the copper catalyst to give a metallocarbene. Both ester and ketone derived phosphoranes can be used, as can styrenyl and non-styrenyl alkenes, which provides cyclopropanes in yields up to 81%.