Search results for "Ethyl diazoacetate"
showing 10 items of 15 documents
Functionalization of CnH2n+2Alkanes: Supercritical Carbon Dioxide Enhances the Reactivity towards Primary Carbon-Hydrogen Bonds
2015
The functionalization of the primary sites of alkanes is one of the more challenging areas in catalysis. In this context, a novel effect has been discovered that is responsible for an enhancement in the reactivity of the primary C-H bonds of alkanes in a catalytic system. The copper complex Cu(NCMe) (=hydrotris{[3,5-bis(trifluoromethyl)-4-bromo]-pyrazol-1-yl}borate) catalyzes the functionalization of CnH2n+2 with ethyl diazoacetate upon inserting the CHCO2Et unit into C-H bonds. In addition, the selectivity of the reaction toward the primary sites significantly increased relative to that obtained in neat alkane upon using supercritical carbon dioxide as the reaction medium. This was attribu…
Favoring alkane primary carbon-hydrogen bond functionalization in supercritical carbon dioxide as reaction medium
2019
The selectivity of a catalytic alkane functionalization process can be modified just changing the reaction medium from neat alkane to supercritical carbon dioxide (scCO2). A silica supported copper complex bearing an Nheterocyclic carbene ligand promotes the functionalization of carbon-hydrogen bonds of alkanes by transferring the CHCO2Et group from N2=CHCO2Et (ethyl diazoacetate, EDA). In neat hexane only 3% of the primary C-H bonds (ethyl heptanoate being the product) are functionalized in that manner, whereas the same reaction carried out in scCO2 provides a 30% yield in this linear ester. Such effect seems to be induced by an electronic density flux from the NHC ligand to the surroundin…
Insight into the mechanism of diazocompounds transformation catalyzed by hetero cuboidal clusters [Mo3CuQ4(MeBPE)3X4]+, (Q=S, Se; X=Cl, Br): The cata…
2008
Abstract Two enantiomerically pure trinuclear compounds of formula (P)-[Mo3S4{(R,R)-Me–BPE}3Br3]Br and (P)-[Mo3Se4{(R,R)-Me–BPE}3Cl3]Cl, (P)-1b.Br and (P)-1c.Cl, respectively, have been synthesized in a good yield and a stereospecific manner by excision of polymeric [Mo3Q7X4]n (Q = S or Se, X = Cl or Br) phases with (R,R)-Me–BPE{1,2-bis[(2R,5R)-2,5-(dimethylphospholan-1-yl)]ethane}. They have been transformed into chiral hetereo cuboidal compounds [Mo3S4{(R,R)-Me–BPE}3Br3]PF6, (P)-2b.PF6, and [Mo3Se4{(R,R)-Me–BPE}3Cl3]PF6, (P)-2c.PF6, by reaction with copper salts. All these compounds have been characterized by 31P NMR, IR, UV–Vis, mass spectrometry, elemental analysis, and chiral dichroism…
Enantio- and Diastereocontrol in Intermolecular Cyclopropanation Reaction of Styrene Catalyzed by Dirhodium(II) Complexes with Bulky ortho-Metalated …
2006
Enantiomerically pure dirhodium(II) complexes with ortho-metalated para-substituted aryl phosphines have been shown to lead to an enantio- and diastereoselective cyclopropanation of styrene with ethyl diazoacetate. Enantioselectivities up to 91% and diastereoselectivities up to 90% are observed for ethyl cis-2-phenylcyclopropanecarboxylate. High enantio- and diastereoselectivities are observed for the synthesis of ethyl cis-2-phenylcyclopropanecarboxylate using water as solvent. Additionally, a (+)-nonlinear effect, (+)-NLE, has been observed and studied in the asymmetric catalytic reaction developed in n-pentane.
Ruthenium titanocene and ruthenium titanium half-sandwich bimetallic complexes in catalytic cyclopropanation
2005
Abstract The reaction of the phosphine functionalised titanium half-sandwich complexes 7, 9 and 10 with the binuclear complex [(p-cymene)RuCl2]2 allowed the access to three new early-late bimetallic complexes (p-cymene)[(μ-η5:η1-C5H4(CH2)nPR2)TiX3]RuCl2 (11–13). The structure of 11 (n = 0, X = Cl) has been confirmed by X-ray diffraction. The ruthenium titanium half-sandwich bimetallic complexes so formed and the ruthenium titanocene analogues 4–6 catalyse the addition of ethyl diazoacetate to styrene with high selectivity toward cyclopropanation versus metathesis contrary to the monometallic complexes (p-cymene)RuCl2PR3.
Unprecedented Stereoselective Synthesis of Catalytically Active Chiral Mo3CuS4 Clusters
2005
Cluster excision of polymeric {Mo3S7Cl4}n phases with chiral phosphane (+)-1,2-bis[(2R,5R)-2,5-(dimethylphospholan-1-yl)]ethane ((R,R)-Me-BPE) or with its enantiomer ((S,S)-Me-BPE) yields the stereoselective formation of the trinuclear cluster complexes [Mo3S4{(R,R)-Me-BPE}3Cl3]+ ([(P)-1]+) and [Mo3S4{(S,S)-Me-BPE}3Cl3]+ ([(M)-1]+), respectively. These complexes possess an incomplete cuboidal structure with the metal atoms defining an equilateral triangle and one capping and three bridging sulfur atoms. The P and M symbols refer to the rotation of the chlorine atoms around the C3 axis, with the capping sulphur atom pointing towards the viewer. Incorporation of copper into these trinuclear c…
Enantiocontrol in the intermolecular cyclopropanation reaction catalyzed by dirhodium(II) complexes with ortho-metalated aryl phosphine ligands
2001
(P) and (M) dirhodium(II) complexes with ortho-metalated aryl phosphines are assessed as chiral catalysts in the enantioselective cyclopropanation of styrenes by ethyl diazoacetate; enantioselectivities up to 91% and up to 87%, respectively, for cis- and trans-2-arylcyclopropanecarboxylates are observed. Barberis, Mario, Mario.Barberis@uv.es ; Lahuerta Peña, Pascual, Pascual.lahuerta@uv.es ; Perez Prieto, Julia, Julia.Perez@uv.es ; Sanau Torrecilla, Mercedes, Mercedes.Sanau@uv.es
Enantio- and diastereocontrol in intermolecular cyclopropanation reaction of styrene catalyzed by dirhodium(II) complexes with bulky ortho-metalated …
2004
Enantiomerically pure dirhodium(II) complexes with ortho-metalated p-substituted aryl phosphines have been shown to be enantio- and diastereoselective in the cyclopropanation of styrene by ethyl diazoacetate. Enantioselectivities up to 91% and diastereoselectivities up to 90% are observed for ethyl cis-2-phenylcyclopropanecarboxylate. Estevan Estevan, Francisco, Francisco.Estevan@uv.es ; Lahuerta Peña, Pascual, Pascual.lahuerta@uv.es ; Lloret Fillol, Julio, Julio.Lloret@uv.es ; Sanau Torrecilla, Mercedes, Mercedes.Sanau@uv.es ; Ubeda Picot, M Angeles, Angeles.Ubeda@uv.es ; Vila Gomez, Jaume Llorenc, Jaume.Vila@uv.es
ortho-Metalated Dirhodium(II) Catalysts Immobilized on a Polymeric Cross-Linked Support by Copolymerization. Study of their Catalytic Activity in the…
2008
Chiral ortho-metalated dirhodium(II) compounds containing the phosphine P(p-CH2═CHC6H4)3 have been efficiently immobilized by radical copolymerization with styrene and 1,4-divinylbenzene. Their cat...
Isomerisierung von 2‐Alkoxycyclopropancarbonsäuren – Eine effektive Synthese von 4‐Oxocarbonsäuren
1983
(Z/E)-2-Alkoxycyclopropansaureester 2/3 werden aus Enolethern 1 und Diazoessigester hergestellt. Durch Verseifen entstehen die (Z/E)-2-Alkoxycyclopropancarbonsauren 4/5, welche in Wasser/Methanol Stereomutation zeigen. Diese Isomerisierung wird an (E)-2-Methoxy-2-phenyl-cyclopropancarbonsaure (5a) in deuterierten Losungsmitteln untersucht und mechanistisch interpretiert. Beim Erwarmen in Wasser/Methanol offnen sich die Verbindungen 4/5 quantitativ zu den entsprechenden 4-Oxocarbonsauren 6. Isomerisation of 2-Alkoxycyclopropanecarboxylic Acids – An Effective Synthesis of 4-Oxo Carboxylic Acids (Z/E)-2-2-Alkoxycyclopropanecarboxylic esters 2/3 were prepared from enol ethers 1 and ethyl diazoa…