Polynaphthylene : Development and Function of Precisely Nano-Structure Controlled Polymer

通过不对称氧化偶联聚合(AOCP)，以高度交叉偶联、选择性或立体可控的方式合成了聚联苯酚。2-萘酚和3-羟基-2-萘酸酯类化合物与CuCl-(S)-2，2‘-isopropylidenebis(4-phenyl-2-oxazoline)[(S)Phbox]催化剂的反应是以高度交叉偶联的方式进行的，具有中等的对映选择性。甲基6，6‘-dihydroxy-2，2’-binaphthalene-7-carboxylate在CuCl-(S)Phbox催化剂上的AOCP反应得到了一种具有高交叉偶联选择性(头尾区域选择性)的聚合物。6，6‘-二羟基-2，2’-联苯和二己基6，6‘-dihydroxy-2，2’-binaphthalene-7，7‘-dicarboxylate的共聚也得到了具有高交叉偶联选择性的聚合物，即具有主要交替结构的共聚物。开发了新型催化体系VOSO4-(R)Phbox，用于2，3-二羟基萘的AOCP反应。聚合过程中的对映体选择性为80%ee(S)，远高于报道的铜(I)基催化体系聚合和典型的氧钒(IV)催化剂催化不对称氧化均偶联合成1，1‘-双-2-萘酚衍生物。通过设计的双核铜(II)络合物催化体系实现了dHN的OCP反应。聚合反应在温和的条件下进行，以较高的产率合成了聚合物。

The asymmetric oxidative coupling polymerization (AOCP) leading to polybinaphthols in a highly cross-coupling selective or stereocontrolled manner was attained. The reaction of 2-naphthol and 3-hydroxy-2-naphthoate derivatives with the CuCl-(S)-2,2'-isopropylidenebis(4-phenyl-2-oxazoline) [(S)Phbox] catalyst proceeded in a highly cross-coupling selective manner with a moderate enantioselectivity. The AOCP of methyl 6,6'-dihydroxy-2,2'-binaphthalene-7-carboxylate with the CuCl-(S)Phbox catalyst gave a polymer with a high cross-coupling selectivity (head-to-tail regioselectivity). The copolymerization of 6,6'-dihydroxy-2,2'-binaphthalene and dihexyl 6,6'-dihydroxy-2,2'-binaphthalene-7,7'-dicarboxylate also afforded a polymer with the high cross-coupling selectivity, that is, a copolymer with a mainly alternating structure. Novel catalyst system, VOSO_4-(R)Phbox, for the AOCP of 2,3-dihydroxy-naphthalene (DHN) was developed. The enantioselectivity during the polymerization was evaluated to be 80% ee (S), a value much higher than that observed for the polymerizations with the copper(I)-based catalyst systems and the typical oxovanadium(IV) catalysts reported for the asymmetric oxidative homo-coupling producing the 1,1'-bi-2-naphthol derivatives. The OCP of DHN was also accomplished by the novel designed catalyst system, dinuclear copper(II) complexes. The polymerization proceeded under mild conditions to produce a polymer in a good yield.