School of Chemistry, University College Dublin, Belfield, D04 V1W8 Dublin 4, Ireland.
Molecules. 2022 Jun 17;27(12):3882. doi: 10.3390/molecules27123882.
The stabilising effect of benzannulation on isoindenes formed in the course of sigmatropic shifts of (CH)Fe(CO) or of organo-silyl groups, and on exocyclic allyl intermediates in the course of haptotropic shifts of organometallic fragments over polycyclic skeletons (fluorene, cyclopenta[]phenanthrene, and dibenzpentalenes) is exemplified. This approach led to the development of the first organometallic molecular brake. Benzyne cycloadditions to anthracenes to form triptycenes also led to unexpected or multiple adducts that were characterised by X-ray crystallography. Synthetic routes to the previously elusive benz[]azulene system are presented. Finally, the complete mechanism of the stepwise assembly of dispiro- and diindenyltetracenes from fluorenylallenes is presented, whereby every intermediate has been unambiguously structurally characterised.
苯并环化稳定了西格玛迁移过程中形成的异茚（isoindenes）和（CH）Fe（CO）或有机硅基团的环外烯丙基中间体，以及在多环骨架（芴、环戊[ ]菲和二苯并戊二烯）中金属有机片段哈普托转移过程中的环外烯丙基中间体。这种方法导致了第一个有机金属分子制动器的发展。苯炔与蒽的环加成反应形成三芴也导致了意想不到的或多加成物，这些加成物通过 X 射线晶体学得到了表征。介绍了以前难以捉摸的苯并[ ]薁系统的合成途径。最后，展示了从芴烯丙基出发逐步组装双螺环和二茚并四烯的完整机制，其中每个中间体都通过结构明确地进行了表征。
