An Ultimate Stereocontrol in Asymmetric Synthesis of Optically Pure Fully Aromatic Helicenes

0446394 - ÚOCHB 2016 RIV US eng J - Článek v odborném periodiku
Šámal, Michal - Chercheja, Serghei - Rybáček, Jiří - Vacek Chocholoušová, Jana - Vacek, Jaroslav - Bednárová, Lucie - Šaman, David - Stará, Irena G. - Starý, Ivo
An Ultimate Stereocontrol in Asymmetric Synthesis of Optically Pure Fully Aromatic Helicenes.
Journal of the American Chemical Society. Roč. 137, č. 26 (2015), s. 8469-8474. ISSN 0002-7863. E-ISSN 1520-5126
Grant CEP: GA ČR GA203/09/1766
Institucionální podpora: RVO:61388963
Klíčová slova: helicenes * asymmetric synthesis * cycloisomerization
Kód oboru RIV: CC - Organická chemie
Impakt faktor: 13.038, rok: 2015

The role of the helicity of small molecules in enantioselective catalysis, molecular recognition, self-assembly, material science, biology, and nanoscience is much less understood than that of point-, axial-, or planar-chiral molecules. To uncover the envisaged potential of helically chiral polyaromatics represented by iconic helicenes, their availability in an optically pure form through asymmetric synthesis is urgently needed. We provide a solution to this problem present since the birth of helicene chemistry in 1956 by developing a general synthetic methodology for the preparation of uniformly enantiopure fully aromatic [5]-, [6]-, and [7]helicenes and their functionalized derivatives. [2 + 2 + 2] Cycloisomerization of chiral triynes combined with asymmetric transformation of the first kind (ultimately controlled by the 1,3-allylic-type strain) is central to this endeavor. The point-to-helical chirality transfer utilizing a traceless chiral auxiliary features a remarkable resistance to diverse structural perturbations.
Trvalý link: http://hdl.handle.net/11104/0248493