Translation of helical chirality from polymer into monomer: supramolecular polymerization of a chirality-memory molecule with an asymmetric Pd(II) complex
Translation of helical chirality from polymer into monomer: supramolecular polymerization of a chirality-memory molecule with an asymmetric Pd(II) complex
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DOI：
10.1016/j.tet.2008.05.126
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发表时间：
2008-09-01
期刊：
影响因子：
2.1
通讯作者：
Aida, Takuzo
中科院分区：
文献类型：
--
作者：
Alam, Md. Akhtarul;Tsuda, Akihiko;Aida, Takuzo
手性记忆鞍形卟啉（1（2 H））在CH（2）Cl（2）中与手性2，2 ′-双（二苯基膦基）-1，1 ′-联萘钯配合物（Pd（II）（BINAP））发生超分子聚合反应，形成具有单手螺旋手性的梯形聚合物（3（2 H））.当将该聚合物倒入含有1，3-双（二苯基膦基）丙烷（DPPP）作为解络剂的AcOH中时，3（2 H）以立体化学保留的方式解聚，得到与AcOH氢键结合的光学活性1（2 H）。尽管由具有两个3-吡啶基苯基内消旋取代基的2（2 H）与Pd（II）（BINAP）结合形成的3（2 H）的环二聚体参照物表现出与3（2 H）类似的行为，但螺旋手性的转化效率低于3（2 H）的情况。(C)2008爱思唯尔有限公司保留所有权利。
A chirality-memorizing saddle-shaped porphyrin (1(2H)) with 3,5-dipyridylphenyl side arms at the opposite meso positions underwent supramolecular polymerization in CH(2)Cl(2) with a chiral Pd(II) complex of 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (Pd(II)(BINAP)), forming a ladder-shaped polymer (3(2H)) with a prevailing one-handed helical chirality. When this polymer was poured into AcOH containing 1,3-bis(diphenylphosphino)propane (DPPP) as a decomplexing agent, 3(2H) was depolymerized in a stereochemically retentive way to give optically active 1(2H), hydrogen-bonded with AcOH. Although a cyclodimeric reference of 3(2H), formed from 2(2H) having two 3-pyridylphenyl meso substituents in conjunction with Pd(II)(BINAP), behaved similar to 3(2H), the translation efficiency of helical chirality was lower than that in the case with 3(2H). (C) 2008 Elsevier Ltd. All rights reserved.