Tris(3,4-dimethylenecyclobuteno)benzene Derivatives with Enhanced Carbon-Carbon Bond-Length Alternation in Annelated Benzene

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• 作者：Kaipeng Hou ; Chenli Wang ; Yunfei Zhou ; Ogunlana Abosede A. and Xiaoguang Bao
• 刊名：European Journal of Organic Chemistry
• 出版年：2016
• 出版时间：September 2016
• 年：2016
• 卷：2016
• 期：25
• 页码：4387-4393
• 全文大小：1328K
• ISSN：1099-0690

文摘

Computational analyses of the tris(3,4-dimethylenecyclobuteno)benzene molecule indicate that the absence of the equivalent of a HOMO of an etheno group between the internal carbon atoms of the annelating butadieno groups is mainly responsible for the relatively weak cyclohexatriene-like fixation in the central benzene ring. To increase the extent of C–C bond-length alternation in the benzene moiety, two strategies of modification of the annelating groups are proposed to make the presence of the equivalent of a HOMO of an etheno group between the internal carbon atoms of the annelating butadieno groups. The first is to introduce a π-electron-donating heteroatom/group to form a five-membered ring with the annelating butadieno groups (model I). The extent of bond-length alternation could be tuned by the choice of the heteroatom/group in model I. The second is to coordinate with transition-metal groups, such as the irontricarbonyl groups, for the annelating butadieno groups (model II). Computational results predict that molecules generated by using these two strategies could form strong cyclohexatriene-like fixation of the double bonds in the central benzene ring.