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Tailoring Diindenochrysene through Intramolecular Multi‐Assemblies by C−F Bond Activation on Aluminum Oxide
Author(s) -
Akhmetov Vladimir,
Feofanov Mikhail,
Troyanov Sergey,
Amsharov Konstantin
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201901450
Subject(s) - intramolecular force , substituent , molecule , oxide , chemistry , carbon fibers , nanotechnology , organic synthesis , combinatorial chemistry , materials science , stereochemistry , catalysis , organic chemistry , composite number , composite material
The unique nature of the alumina‐mediated cyclodehydrofluorination gives the opportunity to execute the preprogrammed algorithm of the C−C couplings rationally built into a precursor. Such multi‐assemblies facilitate the construction of the carbon‐skeleton, superseding the conventional step‐by‐step by the one‐pot intramolecular assembly. In this work, the feasibility of the alumina‐mediated C−F bond activation approach for multi‐assembly is demonstrated on the example of a fundamental bowl‐shaped polycyclic aromatic hydrocarbon (diindenochrysene) through the formation of all “missing” C−C bonds at the last step. Beside valuable insights into the reaction mechanism and the design of the precursors, a facile pathway enabling the two‐step synthesis of diindenochrysene was elaborated, in which five C−C bonds form in a single synthetic step. It is shown that the relative positions of fluorine atoms play a crucial role in the outcome of the assembly and that governing the substituent positions enables the design of effective precursor molecules “programmed” for the consecutive C−C bond formations. In general, these findings push the state of the field towards the facile synthesis of sophisticated bowl‐shaped carbon‐based nanostructures through multi‐assembly of fluoroarenes.