Regiochemical Control in Triptycene Formation-An Exercise in Subtle Balancing Multiple Factors

三蝶烯形成中的区域化学控制——多种因素微妙平衡的实践

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Abstract

Reactions between 1,8-dichloroanthracenes with substituents in position 10 and ortho-chloroaryne afford mixtures of 1,8,13- (syn) and 1,8,16-trichlorotriptycenes (anti). The syn/anti ratio is dependent on these substituents. Electropositive substituents like SiMe(3) and GeMe(3) lead to preferred formation of the syn-isomer, whereas CMe(3) groups exclusively afford the anti-isomer. Different quantum chemical calculations including location of transition states give conflicting results, but indicate the importance of dispersion forces for an at least qualitative prediction of results. The syn-trichlorotriptycenes with SiMe(3) and GeMe(3) substituents were characterized by using NMR spectroscopy, mass spectrometry, and X-ray diffraction experiments.

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