Big Chemical Encyclopedia

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

Articles Figures Tables About

Dipole diradical mechanism

The cycloaddition reaction of dipoles has been known since the late eighteenth century however, before Huisgeris introduction of the concept of a 1,3-dipole, these reactions were considered to proceed via a diradical mechanism [16]. One of the earhest examples of metal-catalyzed 1,3-dipole formation involved the controlled decomposition of an a-dia-... [Pg.433]

The mechanism of the reaction has generally been discussed in terms of a thermally allowed concerted 1,3-dipoIar cycloaddition process, in which control is realized by interaction between the highest occupied molecular orbital (HOMO) of the dipole (diazoalkane) and the lowest unoccupied molecular orbital (LUMO) of the dipolarophile (alkyne).76 In some cases unequal bond formation has been indicated in the transition state, giving a degree of charge separation. Compelling evidence has also been presented for a two-step diradical mechanism for the cycloaddition77 but this issue has yet to be resolved. [Pg.7]

Recently, Huisgen and coworkers have reported on the first unequivocal example of a nonconcerted 1,3-dipolar cycloaddition.27 Sustmann s FMO model of concerted cycloadditions envisions two cases in which the stepwise mechanism might compete with the concerted one.21 Two similar HOMO-LUMO interaction energies correspond to a minimum of rate and a diradical mechanism is possible, especially if stabilizing substituents are present. A second case is when the HOMO (l,3-dipole)-LUMO (dipolarophile) is strongly dominant in the transition state. The higher the difference in rr-MO energies of reac-... [Pg.1073]

The rates of Diels-Alder reactions are little affected by the polarity of the solvent. If a zwitterionic intermediate were involved, the intermediate would be more polar than either of the starting materials, and polar solvents would solvate it more thoroughly. Typically, a large change of solvent dipole moment, from 2.3 to 39, causes an increase in rate by a factor of only 10. In contrast, stepwise ionic cycloadditions take place with increases in rate of several orders of magnitude in polar solvents. This single piece of evidence rules out stepwise ionic pathways for most Diels-Alder reactions, and the only stepwise mechanism left is that involving a diradical. [Pg.31]

An alternative two-step mechanism involving a spin-paired diradical intermediate has also been considered for 1,3-cycloadditions.18,68,69 However, ab initio calculations70-72 on a wide variety of 1,3-dipoles and dipolarophiles are found to coincide essentially with a synchronous 1,3-cycloaddition mechanism.15,17 On the other hand, a two-step mechanism passing through two transition states separated by an intermediate has been derived using the MINDO/3 method, and found to be compatible with substituent and solvent effects as well as stereospecificity observed in 1,3-cycloadditions.73 However, several factors beyond FMO interactions, such as closed shell repulsions, geometrical distortions, polarization, and secondary orbital interactions, all influence mechanisms, rates, and regioselectivities in cycloaddition reactions.74... [Pg.224]

Firestone, on the contrary, on the basis of experimental results and theoretical considerations supported by the Linnett theory, has suggested that both types of 1,3 dipole should follow a two-step mechanism, where one first step, leading to a diradical in a cis or trans conformation, and in a second step this diradical would close to the final five-membered ring, according to Scheme XVII ... [Pg.225]


See other pages where Dipole diradical mechanism is mentioned: [Pg.1083]    [Pg.191]    [Pg.1000]    [Pg.210]    [Pg.82]    [Pg.210]    [Pg.1070]    [Pg.1075]    [Pg.144]    [Pg.20]    [Pg.189]    [Pg.173]    [Pg.256]    [Pg.158]   
See also in sourсe #XX -- [ Pg.433 ]




SEARCH



Dipole mechanism

Dipoles mechanical

Diradical

Diradical mechanism

Diradicals

© 2024 chempedia.info