1995 SYNTEX-AWARD-LECTURE - CORRELATION AND PREDICTION OF RATE CONSTANTS FOR ORGANIC-REACTIONS

Marcus theory provides a framework for correlating rate and equilibriu m constants, and thus the possibility of predicting rate from structur e. This had been successful for a number of simple reactions, includin g the addition of hydroxide to carbonyl compounds, enolate formation f rom carbonyl compounds, and aldol addition and elimination reactions. The theory can be extended, as Multidimensional Marcus Theory, to cove r concerted reactions such as E2 eliminations, the water-mediated prot on switch, or the breakdown of the tetrahedral intermediate in amide h ydrolysis. We have now found that Marcus theory can be applied not onl y to inter-molecular reactions but also to intra-molecular reactions. This is illustrated for aldol condensation and ester/lactone formation .