3589-59-1

Usage

InChI:InChI=1/C10H12N2O4/c1-2-16-10(13)7-11-8-3-5-9(6-4-8)12(14)15/h3-6,11H,2,7H2,1H3

Upstream product

• 105-36-2 ethyl bromoacetate 
• 100-01-6 4-nitro-aniline 
• 300558-35-4 2-(4-tert-butylphenoxy)-N-(4'-nitrophen-1'-yl)acetamide 
• 3598-91-2 N-(4-nitrophenyl)bromoacetamide 
• 623-73-4 diazoacetic acid ethyl ester 
• 201230-82-2 carbon monoxide 

Relevant academic research and scientific papers

Copper-Catalyzed Annulation of Oxime Acetates with α-Amino Acid Ester Derivatives: Synthesis of 3-Sulfonamido/Imino 4-Pyrrolin-2-ones

A copper-catalyzed annulation of oxime acetates and α-amino acid ester derivatives for the easy preparation of 4-pyrrolin-2-ones bearing a 3-amino group has been developed. This process features the oxidation of amines with oxime esters as the internal oxidant to produce the active 1,3-dinucleophilic and 1,2-dielectrophilic species concurrently. The subsequent nucleophilic cyclization realizes the efficient construction of 4-pyrrolin-2-one derivatives.

NH insertion reactions catalyzed by reusable water-soluble ruthenium(II)-hm-phenyloxazoline complex

A water-soluble Ru(II)-hm-pheox complex was efficiently catalyzed NH insertion of EDA with a broad class of amine derivatives in water/ether biphasic medium to deliver the biologically active precursors α-aminoester products with excellent yields (up to >99%). The products were separated by decantation and the catalyst was washed and reused several times (at least 8 times) without any specific loss of its catalytic activity. The plausible mechanism of the reaction was explained. Additionally, In case of ethylene diamine, the NH insertion product could be transformed to biological active piperazinone compound in high yield. The asymmetric version of this catalytic reaction is under investigation.

Dual role of Cu2O nanocubes as templates and networking catalysts for hollow and microporous Fe-porphyrin networks

Cu2O nanocubes were used for the synthesis of hollow and microporous Fe porphyrin networks (H-MFePN). In this synthesis, Cu2O nanocubes performed not only as networking catalysts but also as shape controlling templates. MFePN were formed on the surface of the Cu2O nanocubes through azide-alkyne cycloaddition of tetrakis(4-ethynylphenyl) Fe-porphyrin with 1,4-diazidobenzene. H-MFePN showed excellent catalytic activities in carbene insertion into N-H bonds, maintaining their activities during five recycle tests.

Engineering of RuMb: Toward a Green Catalyst for Carbene Insertion Reactions

The small, stable heme protein myoglobin (Mb) was modified through cofactor substitution and mutagenesis to develop a new catalyst for carbene transfer reactions. The native heme was removed from wild-type Mb and several Mb His64 mutants (H64D, H64A, H64V), and the resulting apoproteins were reconstituted with ruthenium mesoporphyrin IX (RuMpIX). The reconstituted proteins (RuMb) were characterized by UV-vis and circular dichroism spectroscopy and were used as catalysts for the N-H insertion of aniline derivatives and the cyclopropanation of styrene derivatives. The best catalysts for each reaction were able to achieve turnover numbers (TON) up to 520 for the N-H insertion of aniline, and 350 TON for the cyclopropanation of vinyl anisole. Our results show that RuMb is an effective catalyst for N-H insertion, with the potential to further increase the activity and stereoselectivity of the catalyst in future studies. Compared to native Mb ("FeMb"), RuMb is a more active catalyst for carbene transfer reactions, which leads to both heme and protein modification and degradation and, hence, to an overall much-reduced lifetime of the catalyst. This leads to lower TONs for RuMb compared to the iron-containing analogues. Strategies to overcome this limitation are discussed. Finally, comparison is also made to FeH64DMb and FeH64AMb, which have not been previously investigated for carbene transfer reactions.

Reactivity of Me-pma RhI and IrI Complexes upon Deprotonation and Their Application in Catalytic Carbene Carbonylation Reactions

Dehydrogenative oxidation of amines is a relevant process in metal-mediated catalysis, with the amines being either substrates or ligands. Transformation of amine- into imine-type ligands in the coordination sphere of a transition metal can be an important catalyst activation process. The behaviour of secondary pyridin-2-ylmethanamine (pma) ligands in the corresponding rhodium and iridium complexes upon NH deprotonation varies, depending on a number of factors. In this paper the behaviour of the Me-pma ligand [Me-pma = N-methyl-1-(pyridin-2-yl)methanamine] bound to [Rh(cod)]+ and [Ir(cod)]+ was studied. Whereas the iridium amido complex could be obtained upon NH deprotonation, the rhodium complex instantaneously disproportionated into a free pma ligand and an unusual dinuclear complex, adopting a structure with two RhI metal centres hosted by a dianionic (pma-2H)2- ligand, and with the ligand coordinating to Rh2 as an "aza-allyl" fragment. The study gives further proof for the effect of pyridine ligation on the previously observed charge-transfer from the ligand to the metal. Furthermore, the catalytic activity of both the Ir and the Rh species with Me-pma in carbene carbonylation reactions to generate ketenes was studied.

A series of robust metal-porphyrinic frameworks based on rare earth clusters and their application in N-H carbene insertion

We herein report a series of microporous metal-porphyrinic frameworks (MPFs), denoted as NUPF-2M, based on rare earth (RE) clusters. NUPF-2M represent the first examples of RE cluster-based MPFs, possessing a rarely seen shp-a topology and exhibiting high thermal and thermal stabilities. After a post-metallization process with FeCl3, NUPF-2M is catalytically active as an efficient heterogeneous catalyst for intermolecular N-H carbene insertion.

Stable radical cation salt initiated N-H insertion and related proton-transfer-delay three-component reaction

The N-H insertion reaction forms the single addition product exclusively, and does not require slow addition of the diazo component. More importantly, we present the reaction of anilines with both diazoacetates and azodicarboxylates in the presence of catalytic amounts of triarylaminium salt giving the corresponding complex unsymmetrical aminals in high yields. This is the first example of stable radical cation salt promoted proton-transfer-delay three-component reaction.

MYOGLOBIN-BASED CATALYSTS FOR CARBENE TRANSFER REACTIONS

Methods are provided for carrying out carbene transfer transformations such as olefin cyclopropanation reactions, carbene heteroatom-H insertion reactions (heteroatom = N, S, Si), sigmatropic rearrangement reactions, and aldehyde olefination reactions with high efficiency and selectivity by using a novel class of myoglobin-based biocatalysts. These methods are useful for the synthesis of a variety of organic compounds which contain one or more new carbon-carbon or carbon-heteroatom (N, S, or Si) bond. The methods can be applied for conducting these transformations in vitro (i.e., using the biocatalyst in isolated form) and in vivo (i.e., using the biocatalyst in a whole cell system).

Myoglobin-catalyzed intermolecular carbene N-H insertion with arylamine substrates

Engineered variants of the heme-containing protein myoglobin can efficiently catalyze the insertion of α-diazo esters into the N-H bond of arylamines, featuring a combination of high chemoselectivity, elevated turnover numbers, and broad substrate scope.

1-Methylimidazolium tetrafluoroborate [Hmim][BF4]: An efficient acidic ionic liquid catalyst for insertion of α-diazo compounds into the N-H bonds of amines

The reusable acidic ionic liquid, 1-methylimidazolium tetrafluoroborate [Hmim][BF4], was found to be an effective catalyst for the insertion of α-diazoacetate into the N-H bonds of amines. The corresponding products were obtained in good yields and short reaction times via a simple procedure. The catalyst could be recycled and reused without any noticeable decrease in its activity.