Science of Synthesis

Müller, T. J. J., Science of Synthesis: Multicomponent Reactions, (2014) 1, 15.

Pericyclic reactions proceed as concerted processes via cyclic transition states and obey the rules of conservation of orbital symmetry.[‌36‌] The relative energy differences of the interacting frontier molecular orbitals govern the rates of the reactions and the orbital coefficients determine the regioselectivity, for example in the case of cycloadditions.[‌42‌] Most important in planning stereoselective total syntheses is the reliable stereospecificity of pericyclic reactions as well as the high degree of exo/endo diastereoselectivity.[‌55‌] For the design of domino reactions, [4 + 2] and [3 + 2] cycloadditions have received considerable interest and have often been applied in unimolecular sequences leading to complex polycyclic molecular scaffolds.[‌9‌] However, to fall into the range of multicomponent reactions, multiple cycloadditions require that the dienophile or the diene is generated by a preceding bimolecular process.

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References