Jp. Guthrie, 1995 SYNTEX-AWARD-LECTURE - CORRELATION AND PREDICTION OF RATE CONSTANTS FOR ORGANIC-REACTIONS, Canadian journal of chemistry, 74(7), 1996, pp. 1283-1296
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
.