Search results for "Nucleophile"
showing 10 items of 385 documents
ChemInform Abstract: Switchable Palladium-Catalyst Reaction of Bromomethyl Sulfoxides, CO, and N-Nucleophiles: Aminocarbonylation at Csp3versus Oxida…
2013
Pd2(dba)3/ Xantphos-catalyzed coupling of the sulfoxides (I) and (V) with amines and carbon monoxide allows a new and efficient access to amides of type (IV) and (VI).
Reinforced cyclam derivatives functionalized on the bridging unit
2016
International audience; A new synthetic method has been developed for the preparation of reinforced cyclams (1,4,8,11-tetraazacyclotetradecane) C-functionalized on the bridging unit, by using a "one pot" reaction starting from the appropriate bis-aminal cyclam intermediate. The high reactivity of quaternized aminal moiety toward nucleophilic agent has been used to elaborate a new class of cross-bridged and side-bridged cyclam derivatives containing cyanide group on the ethylene bridge. Several chelators and corresponding copper(II) complexes have been prepared and characterized by X-ray diffraction. These new constrained polyazamacrocycles are valuable precursors of bifunctional chelating a…
The domino reaction between 4,6-dinitrobenzofuroxan and cyclopentadiene. Insights on the nature of the molecular mechanism
2004
Abstract The molecular mechanism of the domino reaction between 4,6-dinitrobenzofuroxan, 1 , and cyclopentadiene, Cp, to give the adduct 11 is examined through density functional theory (DFT) calculations at B3LYP/6-31G* level. This domino reaction comprises two consecutive formally [4+2] cycloadditions. The first one is a two-center addition initialized by the nucleophilic attack of Cp to the more electrophilic center of 1 . The subsequent cyclization can take place along two competitive channels associated to the formation of a second C–C bond yielding the formally [2+4] cycloadduct 9 , or a C–O bond yielding the formally [4+2] cycloadduct 10 . The second cycloaddition is a stepwise proce…
Synthesis and reactivity of an 2-azabutadiene-based π-conjugated dithioether: Formation of a N,S-ligated molybdenum chelate complex and C,N,S-pincer …
2005
Abstract Nucleophilic attack of sodium isopropylthiolate on 4,4-dichloro-1,1-diphenyl-2-azabuta-1,3-diene [Cl2C C(H)–N CPh2}] (1) affords the 2-azabutadiene derivative [(i-PrS)2C C(H)–N CPh2] (2). Upon irradiation of Mo(CO)6 in THF in the presence of 2, the chelate complex cis-[(OC)4Mo{(i-PrS)2C C(H)–N CPh2}] (3) is obtained. Coordination on Mo occurs through the imine nitrogen and a thioether group. Polydentate dithioether 2 acts as N,C,S-pincer ligand after orthometallation reaction with Pd(II) or Pt(II). The molecular structures of 2 and (C,N,S)-[(i-PrS)2C C(H)–N C(Ph)C6H4)PtCl] (4b) have been determined by X-ray diffraction studies.
Fluorinated Heterocyclic Compounds− The First Example of an Irreversible Ring-Degenerate Rearrangement on Five-Membered Heterocycles by Attack of an …
2004
The reactions of 5-perfluoroalkyl-1,2,4-oxadiazoles 3 with hydroxylamine in DMF give the regioisomeric 3-perfluoroalkyl-1,2,4-oxadiazoles 4 in excellent yields. This process is the first example of ring-degenerate rearrangement (RDR) occurring on five-membered heterocycles by attack of an external bidentate nucleophile, which replaces two heteroatoms of the ring. We suggest that an ANRORC-like mechanism occurs in which the addition of the nucleophilic nitrogen atom (NH2OH) on the C(5) atom of 3 is followed by ring opening and irreversible ring-degenerate closure by attack of the nucleophilic oxygen atom (=NOH) on the C(3) atom of the original ring, realizing an elegant and efficient synthes…
Palladium C–N bond formation catalysed by air-stable robust polydentate ferrocenylphosphines: a comparative study for the efficient and selective cou…
2014
The arylation of aniline derivatives with dichloroarenes under a low palladium content (below the currently used 5 to 10 mol%) was studied using nine different ferrocenylphosphine ligands, including the easily accessible 1,1′-bis(diphenylphosphino)ferrocene, DPPF. The electron-enriched air-stable tridentate ferrocenylpolyphosphine 1,2-bis(diphenylphosphino)-1′-(diisopropylphosphino)-4-tert-butylferrocene, L5, employed in 2 mol% in combination with 1 mol% [PdCl(η3-C3H5)]2 allows an efficient and selective coupling, while such demanding substrates currently induce chloroarene homocoupling and/or dehalogenation processes. The scope and limitation of the optimized system are explored, with a fo…
2.14 Selected Diastereoselective Reactions: Enolate Alkylation
2012
This chapter discusses processes in which enolates are subjected to reaction with alkylating reagents. In all the processes examined here, at least one of the two reaction components is chiral and the reaction gives rise to one or more diastereomeric compounds. In most cases, the enolate is generated through deprotonation of the corresponding carbonyl precursor with a suitable base, but in several cases, the enolate is generated differently, for example, through Michael addition of a nucleophile to a conjugated carbonyl compound. The various factors that have been found to influence the stereochemical outcome of the alkylation reaction in a measurable way are also discussed. The material ha…
Diastereoselective Synthesis of Dialkylated Bis(phosphino)ferrocenes: Their Use in Promoting Silver-Mediated Nucleophilic Fluorination of Chloroquino…
2017
International audience; The diastereoselective synthesis of dialkylated ferrocenyl bis(phosphane)s bearing aryl, alkyl, and hetero- or polycyclic substituents on the phosphino groups is reported, together with their characterization in the solid state by X-ray structure analysis and in solution by multinuclear NMR spectroscopy. Introduction of various alkyl groups on the ferrocene backbone, namely, tert-butyl, isopropyl, and trimethylsilyl, has a significant influence on the stereoselectivity of the ensuing lithiation/phosphination reactions. Only the introduction of the tert-butyl groups ensures both a high yield and perfect diastereoselectivity, which leads to the exclusive formation of t…
Efficient Nucleophilic Degradation of an Organophosphorus Pesticide “Diazinon” Mediated by Green Solvents and Microwave Heating
2019
An efficient strategy for the degradation of organophosphate pesticide Diazinon was investigated. In this work, ionic liquids, bio-based solvents, and two conventional organic solvents were used as reaction media. Kinetics studies by means of half-life (t1/2,h) were followed by 31P NMR and the products analyzed by GC-MS, HPLC-MS and NMR techniques. These results have shown that t1/2 values in ionic liquids were the lowest and also they were able to activate two electrophilic centers in Diazinon, whilst degradation in bio-based solvents occurred slowly by only an aromatic pathway. In addition, a study to estimate the influence of green activation techniques was carried out by using Ultrasoun…
Electronic fluxes during diels-alder reactions involving 1,2-benzoquinones: mechanistic insights from the analysis of electron localization function …
2012
By means of the joint use of electron localization function (ELF) and Thom's catastrophe theory, a theoretical analysis of the energy profile for the hetero-Diels-Alder reaction of 4-methoxy-1,2-benzoquinone 1 and methoxyethylene 2 has been carried out. The 12 different structural stability domains obtained by the bonding evolution theory have been identified as well as the bifurcation catastrophes (fold and cusp) responsible for the changes in the topology of the system. This analysis permits finding a relationship between the ELF topology and the evolution of the bond breaking/forming processes and electron pair rearrangements through the reaction progress in terms of the different ways o…