Recognition-induced control of a Diels-Alder cycloaddition

The rational design of systems which are capable of accelerating and/or con trolling the stereochemical outcome of the Diels-Alder cycloaddition reacti on between a furan and a maleimide is presented. The origins of the acceler ation and control of the cycloaddition reactions are traced by kinetic stud ies - allied to molecular mechanics calculations - to the formation of comp lexes in which the dienes and the dieneophiles are placed in the appropriat e arrangements for reaction, and, more importantly, to the formation of int ramolecular hydrogen bonds in the cycloadducts. (C) 1999 Elsevier Science L td. All rights reserved.