We report the topochemical syntheses of three polyarylopeptides, wherein triazolylphenyl group is integrated into the backbone of peptide chains. We synthesized three different monomers having azide and arylacetylene as end-groups from glycine, L-alanine and L-valine. We crystallized these monomers and the crystal structures of two of them were determined by single-crystal X-ray diffractometry. Due to the steric constraints, both of these monomers crystallized with two molecules, viz. conformers A and B, in the asymmetric unit. Consistently, in both cases, the A-conformers are antiparallelly π-stacked and B-conformers are parallelly slip-stacked, exploiting weak interactions. Though the arrangements of molecules in the pristine crystals were unsuitable for topochemical reaction, upon heating, they undergo large motion inside the crystal lattice to reach a transient reactive orientation and thereby the self-sorted conformer stacks react to give a blend of triazole-linked polyarylopeptides having two different linkages. Due to the large molecular motion inside crystals, the product phase loses its crystallinity.
Keywords: Arylopeptide; Click Chemistry; Peptidomimetic; Polymerization; Topochemical Reaction.
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