Efficient and Chemoselective Synthesis of 蠅,蠅-Heterodifunctional Polymers

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• 作者：C. Adrian Figg ; Tomohiro Kubo ; Brent S. Sumerlin
• 刊名：ACS Macro Letters
• 出版年：2015
• 出版时间：October 20, 2015
• 年：2015
• 卷：4
• 期：10
• 页码：1114-1118
• 全文大小：375K
• ISSN：2161-1653

文摘

We report a strategy for the preparation of semitelechelic polymers containing two distinct functionalities at one chain end by consecutive and chemoselective nucleophilic aromatic substitution reactions on 2,4,6-trichloro-1,3,5-triazine (TCT). Because of its commercial availability, well-defined nature, and ubiquity in biological applications, monomethyl ether poly(ethylene glycol) (mPEG) was chosen to demonstrate the utility of this 蠅,蠅-heterodifunctional end-group modification strategy. TCT-functionalized mPEG underwent highly efficient 蠅,蠅-heterodisubstitution via sequential chemoselective substitution with model thiols and amines. The efficiency of nucleophile conjugation to the polymer end group was confirmed by ¹H NMR spectroscopy and matrix assisted laser desorption-ionization time-of-flight mass spectrometry. In addition, density functional theory calculations provided insight into the importance of nucleophile addition order. This route introduces TCT derivatization as a powerful and facile tool to achieve specific polymeric end-group complexity and efficient heterogeneous functionalization.