1520-50-9

Upstream product

• 100-42-5 styrene 
• 623-73-4 diazoacetic acid ethyl ester 
• 64-17-5 ethanol 
• 406225-34-1 diethyl 2-(p-toluenesulfonamido)-3-(triphenylphosphoranylidene)butanedioate 
• 1073-67-2 4-vinylbenzyl chloride 
• 637-69-4 4-Methoxystyrene 
• 622-97-9 1-ethenyl-4-methylbenzene 
• 402-50-6 1-trifluoromethyl-4-vinyl-benzene 
• 1746-23-2 4-tert-Butylstyrene 
• 536-74-3 phenylacetylene 
• 98-83-9 isopropenylbenzene 
• 117-80-6 2,3-Dichloro-1,4-naphthoquinone 
• 110-83-8 cyclohexene 
• 100-52-7 benzaldehyde 

Downstream Products

• 213549-53-2 diethyl 3-benzoyl-5-(1,3-dioxolan-2-yl)indolizine-1,2-dicarboxylate 
• 3291-46-1 (2SR,3SR)-oxirane-2,3-dicarboxylic acid diethyl ester 
• 127763-95-5 7-triphenylstannyl-norborn-5-ene-2,3-dicarboxylic acid diethyl ester 
• 78945-64-9 1-phenylpyrrole-3,4-dicarboxylic acid diethyl ester 
• 1186031-49-1 diethyl 7-(4-chlorobenzoyl)-pyrrolo[1,2-b]pyridazine-5,6-dicarboxylate 
• 1186031-48-0 diethyl 7-(4-phenylbenzoyl)-pyrrolo[1,2-b]pyridazine-5,6-dicarboxylate 
• 1186031-50-4 diethyl 7-(3-bromobenzoyl)-pyrrolo[1,2-b]pyridazine-5,6-dicarboxylate 
• 1186031-51-5 diethyl 7-(3-nitrobenzoyl)-pyrrolo[1,2-b]pyridazine-5,6-dicarboxylate 
• 853334-16-4 diethyl 7-(4-nitrobenzoyl)-pyrrolo[1,2-b]pyridazine-5,6-dicarboxylate 
• 1186031-47-9 diethyl 7-benzoyl-pyrrolo[1,2-b]pyridazine-5,6-dicarboxylate 
• 853334-13-1 diethyl 7-(4-bromobenzoyl)-pyrrolo[1,2-b]pyridazine-5,6-dicarboxylate 
• 500011-88-1 2-(3-chloro-pyridin-2-yl)-5-oxo-pyrazolidine-3-carboxylic acid ethyl ester 
• 123-25-1 succinic acid diethyl ester 
• 1329997-61-6 C₂₃H₄₂O₅Si 

Relevant academic research and scientific papers

Controlling the Activity of a Caged Cobalt-Porphyrin-Catalyst in Cyclopropanation Reactions with Peripheral Cage Substituents

In this study, three novel cubic cages were synthesized and utilized to encapsulate a catalytically active cobalt(II) meso-tetra(4-pyridyl)porphyrin guest. The newly developed caged catalysts (Co-G@Fe8(Zn-L ? 1)6, Co-G@Fe8(Zn-L ? 2)6 and Co-G@Fe8(Zn-L ? 3)6) can be easily synthesized and differ in exo-functionalization, which are either none, polar or apolar groups. This leads to a different polarity of the peripheral environment surrounding the cage, which affects the (relative) local concentration of the substrates surrounding the cage and hence indirectly influences the substrate availability of the catalysis embedded in the active site of the caged catalyst systems. The resulting increased local substrate concentrations give rise to higher catalytic activities of the respective caged catalyst in metalloradical catalyzed cyclopropanation reactions. Interestingly, the catalytic activity is the highest when the apolar cage catalyst (Co-G@Fe8(Zn-L ? 1)6) is used, and lowest with the polar analog (Co-G@Fe8(Zn-L ? 3)6). In addition, the catalytic activity of the cage without exo-functionalities (Co-G@Fe8(Zn-L ? 2)6) is nearly two times lower than that of Co-G@Fe8(Zn-L ? 1)6 and three times higher than that of Co-G@Fe8(Zn-L ? 3)6, which further demonstrates the effect of the peripheral functionalities on the cyclopropanation reaction.

Complete control of the chemoselectivity in catalytic carbene transfer reactions from ethyl diazoacetate: An N-heterocyclic carbene-Cu system that suppresses diazo coupling

The complex IPrCuCl (1) catalyzes the transfer of the :CHCO2Et group from ethyl diazoacetate (EDA) to unsaturated and saturated substrates (olefins, amine, alcohols) with very high yields. In the absence of substrate, the complex 1 does not react with EDA to give the diazo coupling products (fumarate and maleate), a rare example in the field of metal-catalyzed diazocompounds decomposition. Copyright

Cyclopropanation and Diels-Alder reactions catalyzed by the first heterobimetallic complexes with bridging phosphinooxazoline ligands

The bimetallic complex trans-[(OC)3Fe(μ-LP,N)2Cu]BF 4(2), which contains two bridging phosphinooxazoline ligands, is the first metal-metal bonded six-membered ring system with P,N donors and its crystal structure shows a unique bimetallic cradle conformation. This complex is an efficient catalyst for the cyclopropanation of styrene by ethyl diazoacetate and for the Diels-Alder reaction between cyclopentadiene and methacrolein, these reactions being catalyzed for the first time by heterometallic complexes.

Poly(ruthenium carbonyl spirobifluorenylporphyrin): A new polymer used as a catalytic device for carbene transfer

Oxidative electropolymerization of tetraspirobifluorenyl porphyrin ruthenium(II) carbonyl complexes can be used to coat Pt electrodes with polymeric films; after being removed from the electrode, these polymeric materials are able to catalyze the heteroge

Wittig reagents as metallocarbene precursors: In situ generated monocarbonyl iodonium ylides

A proof of concept study was undertaken to determine the suitability of monocarbonyl iodonium ylides (MCIYs) as metallocarbene precursors. Exposing Wittig reagents to iodosylbenzene results in a pseudo-Wittig reaction that generates MCIYs in situ. These ylides are intercepted by transition-metal catalysts to generate metallocarbenes, which then undergo either dimerization or cyclopropanation reactions with a variety of alkenes. Additionally, the reaction between diazoester-derived metallocarbenes and Wittig reagents afforded cross-coupling products, illustrating a new type of olefination reaction for phosphonium ylides. Monocarbonyl iodonium ylides (MCIYs) represent a possible alternative to the use diazoketones and -esters as metallocarbene precursors. Upon treatment with iodosylbenzene, a Wittig reagent will undergo ylide transfer to generate a MCIY in situ. In the presence of transition-metal catalysts, MCIYs serve as precursors to metallocarbenes, which undergo dimerization or cyclopropanation of alkenes. tfacac = trifluoroacetylacetonate. Copyright

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.

Ruthenium- and rhodium-catalyzed carbenoid reactions of diazoesters in hexaalkylguanidinium-based ionic liquids

Hexaalkylguanidinium-based room-temperature ionic liquids were investigated as solvents for the cyclopropanation of styrene with diazoacetates catalyzed by Rh2(OAc)4 or [Ru2(μ-OAc) 2(CO)4]n. While the yields of the formed cyclopropanes are much lower compared to the reactions performed in dichloromethane, the diastereomeric ratio is not significantly affected by the change of the reaction medium. Immobilization of the catalysts is only partially successful. In contrast to this intermolecular reaction, the Ru-catalyzed formation of a β-lactam by an intramolecular carbenoid C-H insertion of an α-methoxycarbonyl-α-diazoacetamide occurs in high yield, similar to the Rh2(OAc)4-catalyzed reaction. The cis → trans isomerization of the resulting 1-tert-butyl-3-methoxycarbonyl-4-phenyl-azetidin- 2-one is accelerated in the ionic liquid N,N-dibutyl-N',N'-diethyl-N'',N''- dihexylguanidin-ium triflate.

Catalytic cross-coupling of diazo compounds with coinage metal-based catalysts: An experimental and theoretical study

We examined the ability of TpxM (Tpx = hydrotris(pyrazolyl)borate ligand; M = Cu and Ag) and IPrMCl (IPr = 1,3-bis(diisopropylphenyl)imidazol-2-ylidene; M = Cu, Ag, Au) complexes as catalyst precursors for the cross-coupling of diazo compounds. Experimental data showed that the metal centre can be tuned with the appropriate selection of the ligand to yield either the homo- or hetero-coupling (cross-coupling) products. A computational study of the reaction mechanism allowed the rationalization of the experimental reactivity patterns, and the identification of the key reaction step controlling the selectivity: the initial reaction between the metallocarbene intermediate and one of the diazo compounds.

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.

Cyclobutadiene cobalt complexes as catalysts for insertion of diazo compounds into X–H bonds

Novel cyclobutadiene cobalt complex with labile naphthalene ligand [(C4Et4)Co(C10H8)]PF6 catalyzes the insertion of ethyl diazoacetate into X–H bonds giving the corresponding products in 15–75% yields