Open ends second order reaction

P5.08,11. CLOSED OR OPEN END CONDITIONS. SECOND ORDER REACTION... 

The asymmetric oxidation of organic compounds, especially the epoxidation, dihydroxylation, aminohydroxylation, aziridination, and related reactions have been extensively studied and found widespread applications in the asymmetric synthesis of many important compounds. Like many other asymmetric reactions discussed in other chapters of this book, oxidation systems have been developed and extended steadily over the years in order to attain high stereoselectivity. This chapter on oxidation is organized into several key topics. The first section covers the formation of epoxides from allylic alcohols or their derivatives and the corresponding ring-opening reactions of the thus formed 2,3-epoxy alcohols. The second part deals with dihydroxylation reactions, which can provide diols from olefins. The third section delineates the recently discovered aminohydroxylation of olefins. The fourth topic involves the oxidation of unfunc-tionalized olefins. The chapter ends with a discussion of the oxidation of eno-lates and asymmetric aziridination reactions. 

The initiation step consists of two reactions in series. The first is the production of free radicals, which can be accomplished in many ways. The most common method, however, involves the use of a thermolabile compound, called an initiator (or catalyst), which decomposes to yield fre Radicals when heated. Thus, the homolytic dissociation of an iiiitiator I yields a pair of radicals R, as shown by Eq. (6.3), where kd is the rate constant for initiator dissociation at the particular temperature. Its magnitude is usually of the order of 10 -10 s (Being derived from the initiator, R is referred to as an initiator radical and often as a primary radical.) The second step of the initiation process is the addition of the radical R to a monomer molecule as shown in Eq. (6.4), where RM is the monomer-ended radical containing one monomer unit and an end group R. The rate constant for the reaction is ki. For a vinyl monomer, this second step involves opening the r-bond to form a new radical ... 

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