A Scalable and High‐Yield Strategy for the Synthesis of Sequence‐Defined Macromolecules. Issue 3 (9th December 2015)

• Record Type: Journal Article
• Authors: Solleder, Susanne C.; Zengel, Deniz; Wetzel, Katharina S.; Meier, Michael A. R.
• Is Part Of: Angewandte Chemie international edition. Volume 55:Issue 3(2016)
• Page Start: 1204
• Page End: 1207
• Publication Date: 2015-12-09
• Subjects: metathesis -- multicomponent reactions -- Passerini reaction -- polymers -- sequence control; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201509398
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: The efficient synthesis of a sequence‐defined decamer, its characterization, and its straightforward dimerization through self‐metathesis are described. For this purpose, a monoprotected AB monomer was designed and used to synthesize a decamer bearing ten different and selectable side chains by iterative Passerini three‐component reaction (P‐3CR) and subsequent deprotection. The highly efficient procedure provided excellent yields and allows for the multigram‐scale synthesis of such perfectly defined macromolecules. An olefin was introduced at the end of the synthesis, allowing the self‐metathesis reaction of the resulting decamer to provide a sequence‐defined 20‐mer with a molecular weight of 7046.40 g mol −1 . The obtained oligomers were carefully characterized by NMR and IR spectroscopy, GPC and GPC coupled to ESI‐MS, and mass spectrometry (FAB and orbitrap ESI‐MS). Abstract : Cleary defined : A sequence‐defined decamer with ten different and selectable side chains can be synthesized efficiently (yield of each reaction step >90 %), also on a larger scale, and with simple workup procedures. Functional groups were installed at the side chains allowing for further modification. The self‐metathesis reaction of the sequence‐defined decamer led to a sequence‐defined 20‐mer with a molecular weight of more than 7 kDa.