Design and Enantioresolution of Homochiral Fe(II)-Pd(II) Coordination Cages from Stereolabile Metalloligands: Stereochemical Stability and Enantioselective Separation

被引：110

作者：

Hou, Ya-Jun ^{[1
]}

Wu, Kai ^{[1
]}

Wei, Zhang-Wen ^{[1
]}

Li, Kang ^{[1
]}

Lu, Yu-Lin ^{[1
]}

Zhu, Cheng-Yi ^{[1
]}

Wang, Jing-Si ^{[1
]}

Pan, Mei ^{[1
]}

Jiang, Ji-Jun ^{[1
]}

Li, Guang-Qin ^{[1
]}

Su, Cheng-Yong ^{[1
,2
]}

机构：

[1] Sun Yat Sen Univ, Sch Chem, Lehn Inst Funct Mat, MOE Lab Bioinorgan & Synthet Chem, Guangzhou 510275, Guangdong, Peoples R China

[2] Lanzhou Univ, State Key Lab Appl Organ Chem, Lanzhou 730000, Gansu, Peoples R China

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2018年 / 140卷 / 51期

关键词：

ELECTRON-TRANSFER REACTIONS; METAL-ORGANIC CAGES; ASYMMETRIC-SYNTHESIS; OPTICAL RESOLUTION; TRISPHAT ANIONS; COMPLEX-IONS; RACEMIZATION; CHIRALITY; DISSOCIATION; ENANTIOPURE;

D O I：

10.1021/jacs.8b11152

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The stereochemistry of chiral-at-metal complexes is much more abundant, albeit complicated, than chiral-at-carbon compounds, but how to make use of stereolabile metal-centers remains a formidable challenge due to the highly versatile coordination geometry of metal ions and racemization/epimerization problem. We demonstrate herein a stepwise assembly of configurationally stable [Pd-6(FeL3)(8)](28+) (Delta/Lambda-MOCs-42) homochiral octahedral cages from unstable D-3-symmetry trischelate-Fe type metalloligands via strong face-directed stereochemical coupling and facile chiral-induced resolution processes based on stereo-differentiating host-guest dynamics. Kinetic studies reveal that the dissociation rate of MOC-42 cages is 100-fold slower than that of Fe-metalloligands and the racemization is effectively inhibited, making the cages retain their chirality over extended periods of time (>5 months) at room temperature. Recyclable enantioseparation of atropisomeric compounds has been successfully achieved, giving up to 88% ee.

引用

页码：18183 / 18191

页数：9

共 63 条

[1] MECHANISM OF RACEMIZATION OF COMPLEX IONS .2. KINETICS OF THE DISSOCIATION AND RACEMIZATION OF TRIS-(1,10-PHENANTHROLINE)-IRON(II) AND TRIS-(2,2'-DIPYRIDYL)-IRON(II) COMPLEXES [J].