Precise Synthesis of Molecularly Defined Oligomers and Polymers by Orthogonal Iterative Divergent/Convergent Approaches

The synthesis of perfectly defined (macro)molecules has been a constant challenge for polymer and organic chemists. This paper highlights the main applications of the iterative divergent/convergent approach for the synthesis of discrete mass oligomers and polymers. We will discuss the orthogonal deprotection and coupling strategies involved in this powerful strategy where chain length doubles at each iteration and which has been applied to the synthesis of conjugated rigid rods as well as amorphous and crystalline oligomers and polymers. The synthesis of perfectly defined oligomers in respect to emerging highly efficient and orthogonal chemistries will also be highlighted. By combining orthogonal and highly efficient deprotection and coupling reactions, the iterative divergent/convergent approach is particularly suited for the synthesis of molecularly defined oligomers and polymers. Starting from an orthogonally protected elementary building block, this powerful strategy affords a doubling of the chain length at each deprotection/coupling cycle.