Alkene radical cations, kinetics nucleophiles, reaction with

This review summarizes the generation and spectroscopic characterization of alkene radical cations and kinetic and mechanistic studies of their reactions with nucleophiles and cycloaddition chemistry. Most of the data have been obtained using laser flash photolysis techniques, but comparisons with kinetic data obtained using other methods and with steady-state experiments are presented where appropriate. To date most kinetic measurements using laser Hash photolysis techniques have focused on arylalkene radical cations since these are relatively easy to generate and have spectroscopic and kinetic behavior that is commensurate with nanosecond laser flash photolysis techniques. 

As noted above, most kinetic studies of alkene radical cations in solution have focused on aryl-substituted systems since they have convenient optical propenies and have been extensively studied by other techniques. Radical cations are frequently identified on the basis of their characteristic UV-visible absorptions and the comparison of their spectra to those obtained in matrices at low temperature." However, a number of other diagnostic tests are also commonly employed to identify these intermediates. For example, their kinetic behavior as a function of solvent nucleophilicity or added nucleophiles is analogous to that of other electrophilic species. Thus, reaction with nucleophiles such as azide and halide ions provides support for the assignment of a transient to a radical cation, although it will not serve to eliminate a carbocation intermediate. More useful in the latter respect is the method of generation of the transient since PET does not in general lead to the formation of carbocations. Quenching of the observed transient with a more easily oxidized... 

The reaction of a series of substituted styrene radical cations with anions has recently been studied in detail by laser flash photolysis. Representative kinetic data are summarized in Tables 3 and 4 and demonstrate that most of the anions studied react with styrene radical cations with diffusion controlled rate constants. These reactions can involve either addition to the p-carbon to give a benzyl radical (Eq, 15) as discussed above or electron transfer to regenerate the precursor alkene plus the oxidized nucleophile (NU , Eq. 16). Transient absorption spectra have been used to distinguish between these two possibilities. For example, reaction of the radical cation with either bromide or chloride leads to the formation of a transient that is identified... 

The data for the reactions of four substituted styrene radical cations with selected dienes are summarized in Table 8. - As discussed above for the reaction of styrene radical cations with nucleophiles, the interpretation of these data is complicated by the possibility that two competing reactions are responsible for the observed quenching of the radical cation. One of these is electron transfer from the alkene to the styrene radical cation to generate the neutral styrene and the radical cation of the alkene (Eq. 29). In this case, the quenching rate constant is that for electron transfer, and does not provide any information on the kinetics for the initial addition, although the secondary radical calion/neutral pair may in some cases lead to adduct formation. The other reaction is addition of the alkene to the radical cation to generate an adduct radical cation that is the precursor of the final cyclobutanation and Diels-Alder products (Eq. 30). 

A variety of aryl and diarylalkene radical cations have been generated in solution and characterized using transient absorption spectroscopy. Many of these are sufficiently long-lived for detailed kinetic studies of their intermolecular reactivity under conditions that are comparable to those used in mechanistic and synthetic studies. Reactions with nucleophiles typically occur by either addition or electron transfer, with the latter dominating in cases where the oxidation potential of the nucleophile is lower than that of the alkene. The data summarized herein indicate that most arylalkene radical cations are unseleclive in their additions to anionic nucleophiles in nonprotic solvents. By contrast, the additions to neutral nucleophiles such as alcohols and amines cover a range of timescales and clearly demonstrate the... 

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