A facile synthetic route to stereoregular helical poly(phenyl isocyanide)s with defined pendants and controlled helicity
A facile synthetic route to stereoregular helical poly(phenyl isocyanide)s with defined pendants and controlled helicity
复制标题
具有明确侧链和受控螺旋度的立构规整螺旋聚（苯基异氰）的简便合成路线
DOI：
10.1039/c6py01881e
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发表时间：
2017
影响因子：
4.6
通讯作者：
Wu Zong-Quan
中科院分区：
文献类型：
--
作者：
Yin Jun;Xu Lei;Han Xin;Zhou Li;Li Chonglong;Wu Zong-Quan
使用炔-Pd（II）引发剂的五氟苯基（PFP）酯官能化的苯基异腈（1）的活性聚合提供了具有受控分子量（Mns）和窄分子量分布（Mw/Mns）的明确定义的聚（苯基异腈）。使用醇和胺对这些聚合物进行聚合后改性，形成具有特定酯和酰胺侧基的聚（苯基异腈）。然而，即使当在后修饰反应中使用手性醇和胺时，聚合物也是光学惰性的。有趣的是，使用Pd（II）引发剂的1的活性聚合可以在醇和胺的存在下在一锅中进行。这种一锅聚合导致通过酯或酰胺的连接以高产率形成具有限定侧基的明确限定的螺旋聚（苯基异腈）。值得注意的是，当手性醇和胺用于一锅法聚合时，容易地获得具有优先手性的光学活性螺旋聚（苯异腈）。所得到的螺旋多异腈的光学活性相对较高，并且与通过聚合相应的带有手性酯或酰胺基团的对映体纯苯基异腈单体制备的那些光学活性相当。
The living polymerization of a pentafluorophenyl (PFP) ester-functionalized phenyl isocyanide (1) using an alkyne–Pd(II) initiator affords well-defined poly(phenyl isocyanide)s with controlled molecular weights (Mns) and narrow molecular weight distributions (Mw/Mns). Post-polymerization modification of these polymers using alcohols and amines formed poly(phenyl isocyanide)s with defined ester and amide pendants. However, the polymers are optically inactive even when chiral alcohols and amines were used in the post-modification reactions. Interestingly, living polymerization of 1 using the Pd(II) initiator can be carried out in the presence of alcohols and amines in one-pot. Such one-pot polymerizations lead to the formation of well-defined helical poly(phenyl isocyanide)s in high yields with defined pendants through the linkage of an ester or amide. Remarkably, optically active helical poly(phenyl isocyanide)s with preferred handedness were facilely obtained when chiral alcohols and amines were used in one-pot polymerizations. The optical activities of the afforded helical polyisocyanides were relatively high and comparable to those prepared via polymerization of the corresponding enantiopure phenyl isocyanide monomers bearing chiral ester or amide groups.