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Internal and external factors influencing the Diels–Alder reaction
Author(s) -
Kiselev Vladimir D.,
Konovalov Alexander I.
Publication year - 2009
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.1503
Subject(s) - chemistry , reagent , diels–alder reaction , diene , selectivity , lewis acids and bases , reaction rate , computational chemistry , acceptor , catalysis , organic chemistry , natural rubber , physics , condensed matter physics
The internal and external key factors influencing the reaction rates were considered for the Diels–Alder reaction (DAR) with normal electron demand. A simple dependence lg k 2 = −28.81 +316.3/(IP D − E A )−69.9 R 1–4 /(IP D − E A )−0.054Δ H r‐n for the reaction rate as a function of the ionization potential of π ‐donor dienes, electron affinity of π –acceptor dienophiles, heat of reaction and diene structure ( R 1–4 ) was obtained. This relation allows one to explain the origin of the conventional and ‘anomalous’ relations between activity and selectivity, and the variety of relationships between the kinetic activity and thermodynamic stability. It helps one to choose the conditions for the directed synthesis of desired products, to explain the acceleration effects in the presence of Lewis acids and to predict the rates of the DAR between the different reagents with CC bonds not explored earlier. Copyright © 2009 John Wiley & Sons, Ltd.