Monotelechelic Poly(oxa)norbornenes by Ring-Opening Metathesis Polymerization using Direct End-Capping and Cross Metathesis.
Monotelechelic Poly(oxa)norbornenes by Ring-Opening Metathesis Polymerization using Direct End-Capping and Cross Metathesis.
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DOI：
10.1021/ma9019366
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发表时间：
2010
期刊：
影响因子：
5.5
通讯作者：
Grubbs RH
中科院分区：
文献类型：
--
作者：
Matson JB;Grubbs RH
介绍了两种不同的活性开环易位聚合（ROMP）合成单遥爪聚氧杂环己烯的方法。第一种方法，称为直接封端，通过在活性ROMP反应完成后立即向反应混合物中加入内部顺式烯烃终止剂（TA）来进行。第二种方法依赖于由钌烯烃复分解催化剂（H2IMes）（Cl）2Ru（CH-o-OiPrC6H4）（H2IMes = 1，3-二甲基咪唑烷-2-亚基）介导的亚甲基封端的聚（氧杂）环己烯和顺式烯烃TA之间的交叉复分解（CM）。合成并测试了含有各种官能团的TA，包括醇、乙酸酯、溴化物、α-溴酯、硫代乙酸酯、N-羟基琥珀酰亚胺酯和Boc-胺，以及荧光素和生物素基团。直接封端方法通常导致> 90%的末端官能化效率，而CM方法对于没有极性官能团或显著空间体积的TA几乎同样有效。末端官能化效率值通过1H NMR光谱测定。
Two different methodologies for the synthesis of monotelechelic poly(oxa)norbornenes prepared by living ring-opening metathesis polymerization (ROMP) are presented. The first method, termed direct end-capping, is carried out by adding an internal cis-olefin terminating agent (TA) to the reaction mixture immediately after the completion of the living ROMP reaction. The second method relies on cross metathesis (CM) between a methylene-terminated poly(oxa)norbornene and a cis-olefin TA mediated by the ruthenium olefin metathesis catalyst (H2IMes)(Cl)2Ru(CH-o-OiPrC6H4) (H2IMes = 1,3-dimesitylimidazolidine-2-ylidene). TAs containing various functional groups, including alcohols, acetates, bromides, a-bromoesters, thioacetates, N-hydroxysuccinimidyl esters and Boc-amines, as well as fluorescein and biotin groups, were synthesized and tested. The direct end-capping method typically resulted in >90% end-functionalization efficiency, while the CM method was nearly as effective for TAs without polar functional groups or significant steric bulk. End-functionalization efficiency values were determined by 1H NMR spectroscopy.
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影响因子：
5.5
作者：
Bielawski, CW;Benitez, D;Grubbs, RH
通讯作者：
Grubbs, RH
影响因子：
2.5
作者：
Eren, Tarik;Som, Abhigyan;Tew, Gregory N.
通讯作者：
Tew, Gregory N.
影响因子：
--
作者：
Dag, Aydan;Durmaz, Hakan;Tunca, Umit
通讯作者：
Tunca, Umit
影响因子：
5.5
作者：
FRANCE, MB;GRUBBS, RH;PACIELLO, RA
通讯作者：
PACIELLO, RA
影响因子：
15
作者：
Boydston, Andrew J.;Xia, Yan;Kornfield, Julia A.;Gorodetskaya, Irina A.;Grubbs, Robert H.
通讯作者：
Grubbs, Robert H.