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Carbenes dialkyl

The absolute rate constants for oxygen and sulfur transfer to a range of carbenes (dialkyl, cycloalkylidene, alkylchloro, diaryl, arylchloro, arylalkoxy, and dialkoxy), generated by laser flash photolysis of diazirine or oxadiazoline precursors, were determined. No evidence was seen for ylide formation and a concerted mechanism via an ylide-like transition state was proposed. [Pg.269]

The thermal decomposition of monoanions of tosylhydrazone (Ar = p-tolyl) in a protic solvent like diglyme at 130°C or higher temperature generates dialkyl carbenes. Dialkyl carbenes can also be generated photochemically from salts of tosylhydrazones, but it is difficult to perform the reaction on a large scale. [Pg.93]

Trichloromethyl lithium (generated from BrCCl3 and CH3Li at —100 °C) adds to dialkyl acetylenes and to monoalkyl acetylenes23, thus monoalkyl cyclopropenones became accessible which could not be obtained from terminal acetylenes by reaction with the above carbene sources. The 3,3-dihaIogeno-A1,2-cycIopropenes formed as primary products in the dihalocarbene reactions are usually not isolated, but are hydrolyzed directly to cyclopropenones. [Pg.13]

The most common method for the generation of the metal alkylidene species seems to be a-elimination from an intermediate dialkyl-metal species. This procedure gives the most active catalysts. Above we mentioned the addition of other carbene precursors, which leads to active catalysts. Other methods to generate the metal alkylidene species involve alkylidene transfer from phosphoranes [16] or ring-opening of cyclopropenes [17], In Chapter 16.4 we will describe a few compounds that are active by themselves as metathesis catalysts. [Pg.343]

A broad range of compounds can be O-alkylated with carbene complexes, including primary, secondary, and tertiary alcohols, phenols, enols, hemiaminals, hydroxylamines, carboxylic acids, dialkyl phosphates, etc. When either strongly acidic substrates [1214] and/or sensitive carbene precursors are used (e.g. aliphatic diazoalkanes [1215] or diazoketones) etherification can occur spontaneously without the need for any catalyst, or upon catalysis by Lewis acids [1216]. [Pg.197]

Oxidative decomplexation of the dialkylated organic ligand to provide a butyrolactone is accomplished by successive treatment of the cationic carbene complex with hydroxide followed by bromine96. [Pg.965]

Due the nature of the substituents, all the stable singlet carbenes exihibit some carbon-heteroatom multiple-bond character and for some time their carbene nature has been a subject of controversy. One has to keep in mind that apart from dialkyl-carbenes, all the transient singlet carbenes present similar electronic interactions. As early as 1956, Skell and Garner drew the transient dibromocarbene in its ylide form based on the overlap of the vacant p-orbital of carbon with the filled p orbitals of the bromine atoms (Scheme 8.31). [Pg.365]

Photolysis of dialkyl- and alkyl-diazirines has been broadly investigated since the products formed gave evidence of shortlived intermediates possessing excess vibrational energy. As shown in Scheme 1 diazirines (3) were photoactivated to (235) by irradiation with a medium pressure mercury lamp with quantum yields smaller than one this means reversibly. Nitrogen extrusion yielded carbenes (236). These rearranged to the primary products, alkenes and... [Pg.225]

This topological rule readily explained the reaction product 211 (>90% stereoselectivity) of open-chain nitroolefins 209 with open-chain enamines 210. Seebach and Golinski have further pointed out that several condensation reactions can also be rationalized by using this approach (a) cyclopropane formation from olefin and carbene, (b) Wittig reaction with aldehydes yielding cis olefins, (c) trans-dialkyl oxirane from alkylidene triphenylarsane and aldehydes, (d) ketenes and cyclopentadiene 2+2-addition, le) (E)-silyl-nitronate and aldehydes, (f) syn and anti-Li and B-enolates of ketones, esters, amides and aldehydes, (g) Z-allylboranes and aldehydes, (h) E-alkyl-borane or E-allylchromium derivatives and aldehydes, (i) enamine from cyclohexanone and cinnamic aldehyde, (j) E-enamines and E-nitroolefins and finally, (k) enamines from cycloalkanones and styryl sulfone. [Pg.323]

Both, the Kolbe-Schmitt reaction and the dialkyl carbonate route may be beneficial, notably when taking into account the former syntheses used to produce these carboxylato derivatives. Prior to the study of Tommasi et al., the formation of imi-dazolium carboxylates via highly reactive N-heterocydic carbenes (NHC) had been reported, although this rather challenging synthesis could not be extended to an industrial scale. The synthesis of l,3-diisopropyl-4,5-dimethyl-imidazohum-... [Pg.98]

Dialkyl sulphides are converted into trialkylsulphonium salts by treatment with an alkyl halide (the bromide or iodide is usually the reactant of choice). An important example of this group is trimethylsulphonium iodide, which is used as a methylene transfer reagent by virtue of its being converted in the presence of base into a sulphur ylide, which is a nucleophilic carbene equivalent. [Pg.790]

Imidazolium ligands, in Rh complexes, 7, 126 Imidazolium salts iridium binding, 7, 349 in silver(I) carbene synthesis, 2, 206 Imidazol-2-ylidene carbenes, with tungsten carbonyls, 5, 678 (Imidazol-2-ylidene)gold(I) complexes, preparation, 2, 289 Imidazopyridine, in trinuclear Ru and Os clusters, 6, 727 Imidazo[l,2-a]-pyridines, iodo-substituted, in Grignard reagent preparation, 9, 37—38 Imido alkyl complexes, with tantalum, 5, 118—120 Imido-amido half-sandwich compounds, with tantalum, 5,183 /13-Imido clusters, with trinuclear Ru clusters, 6, 733 Imido complexes with bis-Gp Ti, 4, 579 with monoalkyl Ti(IV), 4, 336 with mono-Gp Ti(IV), 4, 419 with Ru half-sandwiches, 6, 519—520 with tantalum, 5, 110 with titanium(IV) dialkyls, 4, 352 with titanocenes, 4, 566 with tungsten... [Pg.125]

However, an encouraging result was obtained very recently for the 1,4-conjugate addition of dialkyl zinc to a variety of Michael acceptors catalyzed by copper. Alexakis, Roland and coworkers have investigated the addition of diethyl zinc to cycloheptenone and observed an enantiomeric excess of 93% (95% yield) in the presence of Cu(OAc)2 and the silver carbene derivative of imidazolium 1 (Scheme 3) [10]. Silver carbene complexes are efficient transfer agents to copper(II) and therefore the potentially harmful use of a base to generate the catalytic species is avoided. [Pg.120]


See other pages where Carbenes dialkyl is mentioned: [Pg.307]    [Pg.21]    [Pg.187]    [Pg.252]    [Pg.207]    [Pg.290]    [Pg.302]    [Pg.19]    [Pg.227]    [Pg.289]    [Pg.293]    [Pg.92]    [Pg.276]    [Pg.339]    [Pg.1]    [Pg.965]    [Pg.381]    [Pg.381]    [Pg.201]    [Pg.401]    [Pg.1002]    [Pg.21]    [Pg.142]    [Pg.113]    [Pg.1198]    [Pg.188]    [Pg.191]    [Pg.141]    [Pg.245]    [Pg.287]   
See also in sourсe #XX -- [ Pg.226 , Pg.231 ]

See also in sourсe #XX -- [ Pg.226 , Pg.231 ]

See also in sourсe #XX -- [ Pg.226 , Pg.231 ]




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