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Additions to and Substitutions at C-C &pgr;-Bonds, Volume 4 by M.F. Semmelhack

By M.F. Semmelhack

Quantity four makes a speciality of additions and the ensuing substitutions at carbon-carbon &pgr;-bonds. half 1 comprises approaches regularly regarded as basic polar reactions, reactive electrophiles and nucleophiles including to alkenes and alkynes. a big subject is Michael-type addition to electron poor &pgr;-bonds, featured within the first six chapters. partially 2 are amassed the 4 basic methods resulting in nucleophilic fragrant substitution, together with radical chain approaches and transition steel activation via to &pgr;-complexation. Metal-activated addition (generally by way of nucleophiles) to alkenes and polyenes is gifted partially three, together with allylic alkylation catalyzed via palladium. The assurance of nonpolar additions partly four comprises radical additions, organometal addition (Heck reaction), carbene addition, and 1,3-dipolar cycloadditions.

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In this section, we will show how this can be misleading because such rate enhancements are concentration dependent. We will elucidate the parameters which determine the rate enhancement achieved with a kinetic template, by analyzing the thermodynamic and kinetic behavior of simple theoretical models, and applying these models to published template systems. Our theoretical models are similar to the Michaelis-Menten analysis of enzyme catalyzed reactions [5 11, except that we assume there is no catalytic turnover.

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