Allylic derivatives reactivity mechanism

Sigma-bonded transition metal complexes are able to polymerize a range of vinyl monomers, the only limitation being that the monomer should not have groups that react chemically with the transition metal compound. An important observation is that styrene and its derivatives are polymerized by the sigma complexes. In this respect they differ from the jr-allyl compounds that show no reactivity at all toward these monomers. A reasonable explanation for this is that the mechanism of the initiation is different... 

The boron-oxygen mesomeric effect described in the previous section explains the lower reactivity of allylic boronates towards carbonyl compounds compared to that of allylic boranes. The use of Lewis acids, however, allows boronate derivatives, including hindered ones, to react at temperatures comparable to the analogous boranes. As described above (see section Mechanism and Stereochemistry ), the most reactive allylic boronates are those with the most electrophilic boron centers.The nucleophilicity of the y-position of an allylic boron reagent (the position that forms the new C-C bond with the aldehyde) is also important to the reactivity of the reagent. For example, allylic boronates with... 

Bauer G (2000) Reactive oxygen and nitrogen species efficient, selective and interactive signals during intercellular induction of apoptosis. Anticancer Res 20 4115-4140 Beckwith AU, Davies AG, Davison IGE, Maccoll A, Mruzek MH (1989) The mechanisms of the rearrangements of allylic hydroperoxides 5a-hydroperoxy-3p-hydrocholest-6-ene and 7a-hydro-peroxy-3(1-hydroxycholest-5-ene. J Chem Soc Perkin Trans 2 815-824 Behar D, Czapski G, Rabani J, Dorfman LM, Schwarz HA (1970) The acid dissociation constant and decay kinetics of the perhydroxyl radical. J Phys Chem 74 3209-3213 Benjan EV, Font-Sanchis E, Scaiano JC (2001) Lactone-derived carbon-centered radicals formation and reactivity with oxygen. Org Lett 3 4059-4062 Bennett JE, Summers R (1974) Product studies of the mutual termination reactions of sec- alkylper-oxy radicals Evidence for non-cyclic termination. Can J Chem 52 1377-1379 Bennett JE, Brown DM, Mile B (1970) Studies by electron spin resonance of the reactions of alkyl-peroxy radicals, part 2. Equilibrium between alkylperoxy radicals and tetroxide molecules. Trans Faraday Soc 66 397-405... 

The primary factor in S l reactivity is the relative stability of the carbocation that is formed. For simple alkyl halides, this means that only tertiary halides react by this mechanism. The tertiary halide must be able to form a planar carbocation. Only slightly less reactive are the allyl carbocat-ions, which derive their great stability from the delocalization of the charge on the carbon by resonance... 

Grignon, J., Servens, C., Pereyre, M. Reactivity of allylic organotin compounds with halogen derivatives. Synthetic aspects and mechanism. J. Organomet. Chem. 1975, 96, 225-235. 

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