One-pot tandem ring-opening polymerization of N-sulfonyl aziridines and "click" chemistry to produce well-defined star-shaped polyaziridines
One-pot tandem ring-opening polymerization of N-sulfonyl aziridines and "click" chemistry to produce well-defined star-shaped polyaziridines
复制标题
N-磺酰基氮丙啶的一锅串联开环聚合和“点击”化学产生明确的星形聚氮丙啶
DOI：
10.1002/pol.20200154
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发表时间：
2020
影响因子：
3.4
通讯作者：
e
中科院分区：
文献类型：
--
作者：
Luo Wenyi;Wang Ying;Jin Yaocheng;Zhang Zhen;Wu Chu;e
通过N-磺酰基氮丙啶与叠氮三甲基硅（TMSN 3）的一锅串联开环聚合（ROP）和与炔的“点击”反应，快速合成了规整的星星状聚（2-甲基-N-对甲苯磺酰基氮丙啶）.在有机超强碱存在下，N-磺酰基氮杂环丙烷与TMSN 3发生ROP反应，合成了叠氮基封端的聚氮杂环丙烷（α-N3-PAzs）.评价了1，4-二氮杂双环[2.2.2]辛烷（DABCO）、1，8-二氮杂双环[5.4.0]-7-十一碳烯（DBU）、7-甲基-1，5，7-三氮杂双环[4.4.0]癸-5-烯（MTBD）、1，5，7-三氮杂双环[4.4.0]癸-5-烯（TBD）和N，N，N ′，N″，N″-五甲基二亚乙基三胺（PMDETA）等有机碱的催化效率。除TBD外，所有这些化合物均提供了2-甲基-N-甲苯磺酰基氮杂环丙烷（TsMAz）的“活性”/受控ROP。采用一锅串联法快速合成了星星状聚氮丙啶。在反应过程中，PMDETA首先催化ROP，然后通过加入CuBr引发其成为配体进行“点击”反应。成功地制备了结构明确的3臂和4臂星星型P（TsMAz），并将其进行双酰化得到星星型聚丙烯亚胺（PPI）。PPI星表现出固有的光致发光特性的聚胺武器。
An effective approach for fast synthesis of well‐defined star‐shaped poly(2‐methyl‐N‐tosylaziridine)s was developed by one‐pot tandem ring‐opening polymerization (ROP) ofN‐sulfonyl aziridines with trimethylsilyl azide (TMSN3) and “click” reaction with alkynes. Azido terminated polyaziridines (α‐N3‐PAzs) could be achieved via ROP ofN‐sulfonyl aziridines with TMSN3in the presence of organic superbases. The catalytic efficiency of organobases, including 1,4‐diazabicyclo[2.2.2]octane (DABCO), 1,8‐diazabicyclo[5.4.0]‐7‐undecene (DBU), 7‐methyl‐1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (MTBD), 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (TBD), andN,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA), was evaluated, and all of them except TBD afforded “living”/controlled ROP of 2‐methyl‐N‐tosylaziridines (TsMAz). Star‐shaped polyaziridines were then fastly synthesized by the one‐pot tandem strategy. During the reaction process, PMDETA catalyzed ROP first, then was triggered to be a ligand by adding CuBr for “click” reaction. Well‐defined 3‐ and 4‐arm star P(TsMAz)s were successfully prepared, and subsequently desulfonylated to give star‐shaped polypropylenimines (PPIs). PPI stars exhibited intrinsic photoluminescence properties from the polyamine arms.