141-05-9Relevant articles and documents
Maleates from diazoacetates and dilactones from head-to-head dimerisation of alkenyl diazoacetates using Grubbs' 2nd-generation ruthenium carbene catalyst
Hodgson, David M.,Angrish, Deepshikha
, p. 4902 - 4904 (2005)
Grubbs' 2nd-generation ruthenium carbene catalyst homocouples diazoacetates to maleates and also catalyses head-to-head dimerisation of alkenyl diazoacetates giving dienyl dilactones. The Royal Society of Chemistry 2005.
Catalytic Formation of Aziridines from Imines and Diazoacetates
Rasmussen, Kaare G.,Joergensen, Karl Anker
, p. 1401 - 1402 (1995)
A catalytic method for the preparation of aziridines from imines and diazoacetate is developed using copper complexes as catalyst; the synthetic, diastereo- and enantio-selective scope of the reaction are presented.
Cyclopropanation of alkenes with ethyl diazoacetate catalysed by ruthenium porphyrin complexes
Galardon, Erwan,Le Maux, Paul,Simonneaux, Gerard
, p. 927 - 928 (1997)
Ruthenium porphyrin complexes are active catalysts for the cyclopropanation of styrene derivatives by ethyl diazoacetate with good to very good diastereoselectivity; moderate enantiomeric excesses (34%) are observed using a chiral porphyrin as catalyst.
Confinement of Fe-Al-PMOF catalytic sites favours the formation of pyrazoline from ethyl diazoacetate with an unusual sharp increase of selectivity upon recycling
Abeykoon, Brian,Devic, Thomas,Grenèche, Jean-Marc,Fateeva, Alexandra,Sorokin, Alexander B.
, p. 10308 - 10311 (2018)
The catalytic properties of a chemically stable iron porphyrin MOF were evaluated in a reaction with ethyl diazoacetate. In contrast to its homogeneous counterpart, an Fe-porphyrin-MOF features a different reaction pathway leading to the formation of pyrazoline due to the confinement of catalytic sites within the MOF network. Unexpectedly, a sharp increase of the selectivity from 35% (run 1) to 86% (run 5) occurs upon catalyst recycling.
Synthesis and Characterization of Germanium, Tin, Phosphorus, Iron, and Rhodium Complexes of Tris(pentafluorophenyl)corrole, and the Utilization of the Iron and Rhodium Corroles as Cyclopropanation Catalysts
Simkhovich, Liliya,Mahammed, Atif,Goldberg, Israel,Gross, Zeev
, p. 1041 - 1055 (2001)
The germanium(IV), tin(IV), and phosphorus(V) complexes of tris(pentafluorophenyl)corrole were prepared and investigated by electrochemistry for elucidation of the electrochemical HOMO-LUMO gap of the corrole and the spectroscopic characteristics of the corrole ? radical cation. This information was found to be highly valuable for assigning the oxidation states in the various iron corroles that were prepared. Two iron corroles and the rhodium(I) complex of an N-substituted corrole were fully characterized by X-ray crystallography and all the transition metal corroles were examined as cyclopropanation catalysts. All iron (except the NO-ligated) and rhodium corroles are excellent catalysts for Cyclopropanation of styrene, with the latter displaying superior selectivities. An investigation of the effect of the oxidation state of the metal and its ligands leads to the conclusion that for iron corroles the catalytically active form is iron(III), while all accesible oxidation states of rhodium are active.
Mechanochemical defect engineering of HKUST-1 and impact of the resulting defects on carbon dioxide sorption and catalytic cyclopropanation
Barozzino-Consiglio, Gabriella,Filinchuk, Yaroslav,Grégoire, Nicolas,Hermans, Sophie,Steenhaut, Timothy
, p. 19822 - 19831 (2020)
Metal-organic frameworks (MOFs) are recognized as ideal candidates for many applications such as gas sorption and catalysis. For a long time the properties of these materials were thought to essentially arise from their well-defined crystal structures. It is only recently that the importance of structural defects for the properties of MOFs has been evidenced. In this work, salt-assisted and liquid-assisted grinding were used to introduce defects in a copper-based MOF, namely HKUST-1. Different milling times and post-synthetic treatments with alcohols allow introduction of defects in the form of free carboxylic acid groups or reduced copper(i) sites. The nature and the amount of defects were evaluated by spectroscopic methods (FTIR, XPS) as well as TGA and NH3temperature-programmed desorption experiments. The negative impact of free -COOH groups on the catalytic cyclopropanation reaction of ethyl diazoacetate with styrene, as well as on the gravimetric CO2sorption capacities of the materials, was demonstrated. The improvement of the catalytic activity of carboxylic acid containing materials by the presence of CuIsites was also evidenced.
Carbenoid transfer in competing reactions catalyzed by ruthenium complexes
Dragutan, Ileana,Dragutan, Valerian,Verpoort, Francis
, p. 211 - 215 (2014)
Aiming at improving catalyst activity, ten ruthenium promoters have been investigated in carbenoid transfer from ethyl diazoacetate to styrene as a model substrate. Optimal selectivity in cyclopropanation has been attained with the new NHC-Ru complex 10, as well as with the Fischer carbene 7. The surprising non-metathetical behavior of the Grubbs' first-generation catalyst in this multifaceted process is highlighted. Copyright
Catalytic transformations of diazo compounds promoted by platinum(0) and dicationic platinum(II) complexes
Bertani, Roberta,Biasiolo, Monica,Darini, Katia,Michelin, Rino A,Mozzon, Mirto,Visentin, Fabiano,Zanotto, Livio
, p. 32 - 39 (2002)
9-Diazofluorene (DAF) is decomposed either stoichiometrically or catalytically in the presence of the platinum(0) complex [Pt(C2H4)(PPh3)2] to give difluoren-9-ylidene-hydrazine in high yield. Under analogous reaction conditions, diphenyldiazomethane gives mostly the azine, Ph2CNNCPh2, while ethyl diazoacetate (EDA) affords, in low yield, a mixture of diethyl fumarate and maleate in approximately 10:1 molar ratio. The cyclopropanation of styrene with EDA is catalyzed by a series of dicationic complexes of the type [PtL2(NCCH3)2][Y]2 (L2=2PPh3, Ph2PCH=CHPPh2, Ph2PCH2CH2PPh2; Y=BF4, CF3SO3) in 1,2-dichloroethane at 60 °C for 24 h. DAF and EDA undergo insertion reactions into the OH bond of alcohols ROH (R=Me, Et, t-Bu, CH2CHCH2, Ph) at 25 °C in CH2Cl2-ROH (DAF or EDA-ROH molar ratio 1/20) in the presence of 1% mol of several dicationic platinum(II) complexes to give the corresponding ethers in excellent yields.
Continuous flow asymmetric cyclopropanation reactions using Cu(i) complexes of Pc-L* ligands supported on silica as catalysts with carbon dioxide as a carrier
Castano, Brunilde,Gallo, Emma,Cole-Hamilton, David J.,Dal Santo, Vladimiro,Psaro, Rinaldo,Caselli, Alessandro
, p. 3202 - 3209 (2014)
Continuous flow heterogeneous asymmetric cyclopropanations catalysed by supported hydrogen-bonded (SHB) chiral copper(i) complexes of pyridine containing tetraazamacrocyclic ligands Pc-L* using CO2 as a transport vector are described. The catalytic system showed high stability and good recyclability without loss of activity for at least 24 h in CO2 and catalyst turnover numbers up to 440 were obtained with excellent conversion (up to 99%) and high selectivity (up to 88%). No leaching of copper was observed. Cyclopropane products from both aromatic and aliphatic olefins were obtained in good yields with enantiomeric excesses up to 72%. This journal is the Partner Organisations 2014.
Cobalt carbaporphyrin-catalyzed cyclopropanation
Fields, Kimberly B.,Engle, James T.,Sripothongnak, Saovalak,Kim, Chungsik,Zhang, X. Peter,Ziegler, Christopher J.
, p. 749 - 751 (2011)
Cobalt complexes of N-confused porphyrins and benziphthalocyanine, which both feature organometallic bonds at the macrocycle cores, catalyze the cyclopropanation of styrene with a higher trans-selectivity than the corresponding porphyrin and phthalocyanine complexes. The Royal Society of Chemistry 2011.
