Separation of enantiomers on diastereomeric right- and left-handed helical poly(phenyl isocyanide)s bearing L-alanine pendants immobilized on silica gel by HPLC
Separation of enantiomers on diastereomeric right- and left-handed helical poly(phenyl isocyanide)s bearing L-alanine pendants immobilized on silica gel by HPLC
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DOI：
10.1039/c0py00164c
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发表时间：
2011
影响因子：
4.6
通讯作者：
Kazumi Tamura;Toshitaka Miyabe;Hiroki Iida;E. Yashima
中科院分区：
文献类型：
--
作者：
Kazumi Tamura;Toshitaka Miyabe;Hiroki Iida;E. Yashima
制备了由L-丙氨酸键合的苯基异腈组成的非对映体左旋和右旋螺旋多异腈。将分子量分布窄的螺旋聚合物通过化学键合固定在硅胶载体上，并将其作为高效液相色谱手性固定相（CSPs）进行了光学拆分性能的评价。由左旋螺旋多异氰酸酯制备的CSP拆分外消旋环醚和羰基化合物以及环状二酰苯胺和二苯甲酰胺，而右旋螺旋多异氰酸酯基CSP显示出相当互补的手性识别能力，并且特异性地拆分外消旋金属乙酰丙酮络合物，这些化合物在前CSP上根本不分离。此外，一些对映体的洗脱顺序是相反的CSP，从而表明，大分子螺旋的L-丙氨酸结合的多异腈发挥了关键作用的对映体的对映选择性和洗脱顺序。
Diastereomeric left- and right-handed helical polyisocyanides composed of L-alanine-bound phenyl isocyanides were prepared. The helical polymers with a narrow molecular weight distribution were immobilized on a silica gel support via chemical bonding and their optical resolution abilities were evaluated as chiral stationary phases (CSPs) for high-performance liquid chromatography (HPLC). The CSP prepared from the left-handed helical polyisocyanide resolved racemic cyclic ether and carbonyl compounds and cyclic dianilides and dibenzamides, whereas the right-handed helical polyisocyanide-based CSP showed a rather complementary chiral recognition ability and specifically resolved racemic metal acetylacetonate complexes, which were not separated on the former CSP at all. Additionally, the elution order of some enantiomers was reversed on the CSPs, thus indicating that the macromolecular helicity of the L-alanine-bound-polyisocyanides played a critical role in the enantioselectivity and elution order of the enantiomers.