The Principle of Non-perfect Synchronization
作者： Claude F. Bernasconi
DOI: 10.1016/S0065-3160(08)60065-9
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摘要: Publisher Summary This chapter focuses on the principle of non-perfect synchronization (PNS), a prime example physical organic concept that deals with chemical reactivity in qualitative or semiquantitative way. The basic idea PNS is to relate certain features transitionstate structure, deduced from substituent solvent effects rates and equilibria, reactivity. describes relationship between intrinsic rate constants transition-state imbalances. transition state majority reactions has potential for being imbalanced. Among factors, only ones appear develop ahead bond formation are soft acid–soft base interaction nucleophile electrophile thiolate ion additions olefins, steric effects. In view universality PNS, it would expect also operates enzyme catalyzed reactions. No systematic studies have been performed area specifically address contribution by avoidance
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