Synthesis of Chiral Non-Racemic Dimers and Polymers Via Topochemical Reactions in Chiral Crystals; an Example of an ‘Absolute’ Asymmetric Synthesis

Abstract

The asymmetric synthesis of chiral polymers by topochemically controlled polymerization in chiral crystals is discussed. Following a short survey of topochemical polymerization in the solid state and some comments on chiral crystals, we present the requirements for the performance of asymmetric polymerization based on [2+2]-photocycloaddition. The planning and execution of two successful polymerizations of this sort are described. In the first, we start with a chiral non-racemic monomer and obtain optically active cyclobutane oligomers. The optical yields of the dimer and trimer were quantitative on the scale of N.M.R. sensitivity. In the second reaction we start with a racemate, and by the processes of crystallization in a chiral structure and solid-state reaction we generate an optically active polymer, in the absence of any outside chiral agent. The possible application of this novel method to additional systems is discussed.