Big Chemical Encyclopedia

Chemical substances, components, reactions, process design ...

Articles Figures Tables About

Insertion-abstraction, carbene

The mechanism of 0-H bond insertion by carbenes remains an intense held of investigation. In the case of ether formation, three distinct pathways can be proposed (i) abstraction of protons from the alcohol forming an intermediate ion pair, (ii) reaction with the oxygen atom of an alcohol forming an intermediate ylide, and (hi) direct (concerted) insertion into the O-H bond. In that context, the carbene - alcohol ylide resulting from the reaction between carboethoxycarbene and MeOD has been experimentally detected for the first time, thus corroborating the viability of the ylide pathway. ... [Pg.215]

CO insertion p-hydrogen ehmination agostic M H C interaction a-hydrogen abstraction carbene (alkylidene) carbyne (alkylidyne) sandwich complex metallocene half-sandwich complex... [Pg.934]

Carbenes can react either (1) intramolecularly or (2) intermolecularly. The basic reactions are addition and insertion. Triplet carbenes can also react via an abstraction mechanism. As typical examples, the intra- and intermolecular reactions with a double bond are shown in Schemes 4 and 5, respectively. [Pg.1840]

Abstract The photoinduced reactions of metal carbene complexes, particularly Group 6 Fischer carbenes, are comprehensively presented in this chapter with a complete listing of published examples. A majority of these processes involve CO insertion to produce species that have ketene-like reactivity. Cyclo addition reactions presented include reaction with imines to form /1-lactams, with alkenes to form cyclobutanones, with aldehydes to form /1-lactones, and with azoarenes to form diazetidinones. Photoinduced benzannulation processes are included. Reactions involving nucleophilic attack to form esters, amino acids, peptides, allenes, acylated arenes, and aza-Cope rearrangement products are detailed. A number of photoinduced reactions of carbenes do not involve CO insertion. These include reactions with sulfur ylides and sulfilimines, cyclopropanation, 1,3-dipolar cycloadditions, and acyl migrations. [Pg.157]

Abstract The dirhodium(II) core is a template onto which both achiral and chiral ligands are placed so that four exist in a paddle wheel fashion around the core. The resulting structures are effective electrophilic catalysts for diazo decomposition in reactions that involve metal carbene intermediates. High selectivities are achieved in transformations ranging from addition to insertion and association. The syntheses of natural products and compounds of biological interest have employed these catalysts and methods with increasing frequency. [Pg.203]

That this mechanism can take place under suitable conditions has been demonstrated by isotopic labeling and by other means. However, the formation of disproportionation and dimerization products does not always mean that the free-radical abstraction process takes place. In some cases these products arise in a different manner.We have seen that the product of the reaction between a carbene and a molecule may have excess energy (p. 247). Therefore it is possible for the substrate and the carbene to react by mechanism 1 (the direct-insertion process) and for the excess energy to cause the compound thus formed to cleave to free radicals. When this pathway is in operation, the free radicals are formed after the actual insertion reaction. [Pg.790]

This key paper was followed by a flurry of activity in this area, spanning several years." " "" A variety of workers reported attempts to deconvolute the temperature dependence of carbene singlet/triplet equilibria and relative reactivities from the influence of solid matrices. Invariably, in low-temperature solids, H-abstraction reactions were found to predominate over other processes. Somewhat similar results were obtained in studies of the temperature and phase dependency of the selectivity of C-H insertion reactions in alkanes. While, for example, primary versus tertiary C-H abstraction became increasingly selective as the temperature was lowered in solution, the reactions became dramatically less selective in the solid phase as temperatures were lowered further. Similar work of Tomioka and co-workers explored variations of OH (singlet reaction) versus C-H (triplet reaction) carbene insertions with alcohols as a function of temperature and medium. Numerous attempts were made in these reports to explain the results based on increases in triplet carbene population... [Pg.435]

Singlet Carbene C-H Insertions Although [1,2]-H shifts are formally carbene C-H insertions, these rearrangements have different orbital symmetry aspects than those of intramolecular insertions. As described above, overwhelming evidence exists that triplet carbenes undergo abstraction-recombination reactions to... [Pg.446]

The olefinic products which formally correspond to C—H insertion reactions are thought to arise by stepwise abstraction of hydrogen by triplet carbene and subsequent recombination ... [Pg.554]

The mechanism of the insertion is not clear, however, since both carbenes have triplet ground states, an abstraction-recombination mechanism with radical pairs as intermediates is most likely. The only other triplet carbene that has been reported to insert into CH4 in low temperature matrices is methylene.89,90 However, in this case it is not completely clear if the insertion is a thermal or photochemical reaction. [Pg.185]

The four hitherto known routes of the C-H insertion are shown in Scheme 1. In general, the insertion by singlet carbenes proceeds via route a in one step, whereas the reaction by triplet carbenes proceeds sequentially via route b, i.e., hydrogen abstraction followed by recombination of the radical pairs.4 Other stepwise mechanisms are hydride abstraction (route c) and proton abstraction (route d), both being followed by the recombination of ion pairs. However, extended study on routes c and d for synthetic purposes had not been done before we started, except for a few earlier studies on carbanion-promoted P C-H insertion reactions.5,6 Recent advances in transition metal-catalyzed... [Pg.288]

Since alkyllithium compounds and their carbanions have an isoelectronic structure with alkoxides, their reaction behavior with carbenes is expected to be similar to that of alkoxides, showing enhanced reactivity in both C-H insertion and hydride abstraction.35 In this reaction, the hydride abstraction cannot be followed by recombination and, therefore, can be differentiated from the insertion. Indeed, the reaction of alkyllithium compounds 70 or nitrile anions (see Section IV.B) with ethyl(phenylthio)carbenoid, which is generated by the reaction of 1-chloropropyl sulfide 69 with BuLi, takes place at the -position of 70 more or less in a similar manner giving both insertion product 71 and hydride abstraction products 72 and 73, respectively. This again supports a general rule C-H bonds at the vicinal position of a negatively charged atom are activated toward carbene insertion reactions (Scheme 22). [Pg.309]

A second process that has a central position in the analysis of the chemical properties of carbenes is their reaction with hydrocarbons. As is the case for alcohols, singlet and triplet carbenes react with hydrocarbons in distinctive ways. It has long been held that very electrophilic singlet carbenes can insert directly into carbon-hydrogen bonds (11) (Kirmse, 1971). On the other hand, triplet carbenes are believed to abstract hydrogen atoms to generate radicals that go on to combine and disproportionate in subsequent steps (12)... [Pg.328]

Xanthylidene does not react measurably with cyclohexane at room temperature (Table 5). Thermolysis of DAX at high temperature does, however, give some of the expected coupling product 9-cyclohexylxanthene. The crossover experiment (1 1 C6H12, C6D12) reveals that this product is not formed by the abstraction-recombination sequence. This observation is consistent with the direct insertion characteristic of a singlet carbene. [Pg.340]

Irradiation of DMDAF in cyclohexane solution gives mainly insertion and only very minor amounts of the coupling and disproportionation products expected if hydrogen-atom abstraction were a major process. The lifetime of the carbene in cyclohexane is ca 11 ns and increases to 19 ns in C6D12. When the irradiation is performed in a 1 1 mixture of C6H12 and C6D12 the insertion product shows no crossover (Table 5). These chemical properties are those normally associated with a singlet carbene. [Pg.344]

The mechanism proposed for carbene-abstraction and carbene-insertion reactions is based on the calculations of Dewar (MINDO/2) and Hoffmann (extended Hiickel) Hoffmann dealt only with the concerted reactions of singlet carbenes, whereas Dewar discussed both singlet and triplet carbene reactions. The calculations of Dewar s ) for the reaction of triplet methylene with methane gave the following results ... [Pg.107]

Evident cases of abstraction/recombination mechanism are observed with phenylsubstituted carbenes. Diphenyl-diazomethane, which is photolyzed to give the triplet diphenyl-carbene, very readily abstracts a hydrogen atom from the benzyl group of toluene. The primarily formed radicals can now recombine to give a formal "insertion product — 1,1,2-triphenylethane — or they can recombine to form 1,1,2,2-tetraphenylethane and 1,2-diphenylethane... [Pg.109]


See other pages where Insertion-abstraction, carbene is mentioned: [Pg.62]    [Pg.335]    [Pg.335]    [Pg.337]    [Pg.339]    [Pg.341]    [Pg.343]    [Pg.365]    [Pg.21]    [Pg.102]    [Pg.100]    [Pg.791]    [Pg.113]    [Pg.434]    [Pg.437]    [Pg.439]    [Pg.453]    [Pg.224]    [Pg.302]    [Pg.313]    [Pg.334]    [Pg.352]    [Pg.318]    [Pg.37]    [Pg.97]    [Pg.192]    [Pg.111]   


SEARCH



Abstraction-recombination insertion triplet carbenes

Carbene insertion

Carbenes abstraction

Carbenes insertion

Carbenes insertion-abstraction

Carbenes insertion-abstraction

Insertion reactions triplet carbenes, hydrogen abstraction, product

Insertion, Abstraction, and Rearrangement Reactions of Carbenes

© 2024 chempedia.info