Abstract
Most of the reactions described in the preceding chapters involve polar or polarizable reactants and proceed through polar intermediates or transition states. One reactant can be identified as nucleophilic, and the other as electrophilic. Carbanion alkylations, nucleophilic additions to carbonyl groups, and electrophilic additions to alkenes are examples of such reactions. The reactions to be examined in this chapter, on the other hand, occur by a reorganization of valence electrons through activated complexes that are not much more polar than the reactants. These reactions usually proceed through cyclic transition states, and little separation of charge occurs during these processes. The energy necessary to attain the transition state is usually provided by thermal or photochemical excitation of the reactant(s), and frequently no other reagents are involved. Many of the transformations fall into the category of concerted pericyclic reactions, and the transition states are stabilized by favorable orbital interactions, as discussed in Chapter 11 of Part A. We will also discuss some reactions which effect closely related transformations but which, on mechanistic scrutiny, are found to proceed through discrete intermediates.
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Carey, F.A., Sundberg, R.J. (2001). Cycloadditions, Unimolecular Rearrangements, and Thermal Eliminations. In: Part B: Reactions and Synthesis. Advanced Organic Chemistry, vol Pt. B. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-662-39510-3_6
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