[6]Saddlequat: a [6]helquat captured on its racemization pathway

被引：31

作者：

Adriaenssens, Louis ^{[1
]}

Severa, Lukas ^{[1
]}

Koval, Dusan ^{[1
]}

Cisarova, Ivana ^{[2
]}

Martinez Belmonte, Marta ^{[3
]}

Escudero-Adan, Eduardo C. ^{[3
]}

Novotna, Pavlina ^{[4
]}

Sazelova, Petra ^{[1
]}

Vavra, Jan ^{[1
]}

Pohl, Radek ^{[1
]}

Saman, David ^{[1
]}

Urbanova, Marie ^{[5
]}

Kasicka, Vaclav ^{[1
]}

Teply, Filip ^{[1
]}

机构：

[1] Acad Sci Czech Republ, Inst Organ Chem & Biochem, Vvi, CR-16610 Prague, Czech Republic

[2] Charles Univ Prague, Dept Inorgan Chem, CR-12840 Prague, Czech Republic

[3] Inst Chem Res Catalonia ICIQ, Tarragona, Spain

[4] Inst Chem Technol, Dept Analyt Chem, CR-16628 Prague, Czech Republic

[5] Inst Chem Technol, Dept Phys & Measurements, CR-16628 Prague, Czech Republic

来源：

CHEMICAL SCIENCE | 2011年 / 2卷 / 12期

关键词：

PYRIDINE N-OXIDES; THERMAL RACEMIZATION; ASYMMETRIC-SYNTHESIS; ENANTIOSELECTIVE SYNTHESIS; 2+2+2 CYCLOISOMERIZATION; CHIROPTICAL PROPERTIES; CHIRAL DISCRIMINATION; CATALYZED SYNTHESIS; MOLECULAR MACHINES; CRYSTAL-STRUCTURES;

D O I：

10.1039/c1sc00468a

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A dicationic [6]helicene congener captured on the racemization pathway in its saddle-shaped geometry is introduced. Synthesis, structure, resolution, and dynamic properties of this chiral [6]saddlequat in-between and its highly stereocontrolled transformation into enantiopure [6]helquat are discussed and demonstrated. The dynamic aspects established by experiment and supported by detailed DFT-D calculations are presented visually in the form of a movie (electronic table-of-contents and electronic supplementary information). The title [6]saddlequat was found to be an isolable chiral species on the entirely chiral enantiomerization pathway of a [6]helquat that is discussed as an example of Mislow's "rubber glove'' molecule.

引用

页码：2314 / 2320

页数：7

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