Functionalization of Azapentabenzocorannulenes by Fivefold C-H Borylation and Cross-Coupling Arylation: Application to Columnar Liquid-Crystalline Materials.

@article{Nagano2018FunctionalizationOA,
  title={Functionalization of Azapentabenzocorannulenes by Fivefold C-H Borylation and Cross-Coupling Arylation: Application to Columnar Liquid-Crystalline Materials.},
  author={Taro Nagano and Kimihiro Nakamura and Yuki Tokimaru and Shingo Ito and Daigo Miyajima and Takuzo Aida and Kyoko Nozaki},
  journal={Chemistry},
  year={2018},
  volume={24 53},
  pages={
          14075-14078
        }
}
Herein, the one-shot fivefold functionalization of azapentabenzocorannulenes by an iridium-catalyzed fivefold C-H borylation reaction that exhibits excellent regioselectivity is reported. The borylated product can be used as a versatile synthetic intermediate for further derivatization via Suzuki-Miyaura cross-coupling reactions. This fivefold borylation/arylation sequence was employed to synthesize liquid-crystalline azapentabenzocorannulenes with five 3,4,5-trialkoxyphenyl groups, which… 
17 Citations
Synthesis of π-Extended Imidazoles by 1,3-Dipolar Cycloaddition of Polycyclic Aromatic Azomethine Ylides with Nitriles.
TLDR
The 1,3-dipolar cycloaddition of polycyclic aromatic azomethine ylides with nitriles is reported to produce highly fused imidazole derivatives, that is, tribenzo[b,g,ij]imidazo[2,1,5-de]quinolizine and palladium-catalyzed intramolecular cyclization provides an efficient approach to further π-extendedImidazoles.
On-Surface Synthesis of a π-Extended Diaza[8]circulene.
TLDR
The first example of a π-extended diaza[8]circulene surrounded by and fused with six hexagons and two pentagons, which was successfully synthesized only by a combined in-solution and on-surface synthetic strategy is described.
Recent Advances in Heterocyclic Nanographenes and Other Polycyclic Heteroaromatic Compounds
TLDR
This review surveys recent progress in the chemistry of polycyclic heteroaromatic molecules with a focus on structural diversity and synthetic methodology, providing an update to the first review of this topic in 2017.
C-H Acyloxylation of Polycyclic Aromatic Hydrocarbons.
TLDR
The C-H acyloxylation of polycyclic aromatic hydrocarbons (PAHs) is described and the synthesis of structurally new symmetric and unsymmetric diaroyloxylated fluoranthenes was accomplished with a ruthenium photoredox catalyst.
An Isosteric Triaza Analogue of a Polycyclic Aromatic Hydrocarbon Monkey Saddle
TLDR
The synthesis of the aza analogue has a significantly higher inversion barrier, which makes it easier to handle at room temperature and the influence of this CH↔N exchange on photophysical and electrochemical properties is studied.
Stepwise Reduction of Azapentabenzocorannulene.
TLDR
The present study provides the first successful isolation and characterization of the reduced products of heteroatom-containing buckybowl molecules.
Recent Advances in C–H Activation for the Synthesis of π-Extended Materials
The activation of typically unreactive aromatic C–H bonds by transition-metal catalysis has been receiving increased attention from the synthetic chemistry community in recent years. Advances in th...
Satellite-Dish-Shaped Pentagon- and Heptagon-Embedded Nanographene Build on a Central Pyrrolo[3,2-b]pyrrole Core.
TLDR
This synthesis represents the first case of programmed sequential intramolecular direct arylation reactions utilizing the different reactivity of C-Br and C-Cl bonds.
The art of two-dimensional soft nanomaterials
The discovery of graphene has triggered the explosive development of two-dimensional (2D) nanomaterials, including both inorganic and organic species. Benefiting from the simple elemental
...
...

References

SHOWING 1-10 OF 53 REFERENCES
Regioselectivity of the borylation of alkanes and arenes.
  • J. Hartwig
  • Chemistry, Biology
    Chemical Society reviews
  • 2011
TLDR
The borylation of alkanes and arenes has become some of the most practical C-H bond functionalization chemistry, and the high regioselectivity of these reactions is described in this critical review.
Pushing the Ir-catalyzed C-H polyborylation of aromatic compounds to maximum capacity by exploiting reversibility.
TLDR
A high-yield, one-step synthesis of 1,3,5,7,9-pentakis(Bpin)corannulene is reported that illustrates this useful extension of the Ir-catalyzed borylation reaction.
Benzene-Fused Azacorannulene Bearing an Internal Nitrogen Atom.
TLDR
This molecule represents the first example of a corannulene derivative bearing an internal heteroatom, and exhibits unique structural and physical properties caused by the introduction of the nitrogen atom and extended π-conjugation, as compared to the parent corannULene.
Borylation and silylation of C-H bonds: a platform for diverse C-H bond functionalizations.
  • J. Hartwig
  • Chemistry
    Accounts of chemical research
  • 2012
TLDR
The fundamental principles that govern the reactivity of intermediates containing metal-boron bonds are emphasized and how an understanding of the effects of the ligands on this reactivity led us to broaden the scope of main group reagents that react under mild conditions to generate synthetically useful organosilanes is described.
Selective Ir-catalysed borylation of polycyclic aromatic hydrocarbons: structures of naphthalene-2,6-bis(boronate), pyrene-2,7-bis(boronate) and perylene-2,5,8,11-tetra(boronate) esters.
The selectivity of the iridium boryl complex-catalysed reaction of pyrene and perylene with B2(pin)2 (pin = OCMe2CMe2O) has been employed in the synthesis of D(2h)-symmetry pyrene-2,7-(Bpin)2 and
1,3,5,7-Tetra(Bpin)azulene by Exhaustive Direct Borylation of Azulene and 5,7-Di(Bpin)azulene by Selective Subsequent Deborylation
Exhaustive borylation of azulene with excess bis(pinacolato)-diboron (B2pin2) under conditions that promote equilibration of the borylated azulenes provides a convenient one-step synthesis of
Fourfold C–H Borylation of Anthracene: 1,3,5,7-Tetraborylanthracene and Its Application to 1,3,5,7-Tetraarylanthracenes
Iridium-catalyzed direct tetraborylation of anthracene to give 1,3,5,7-tetrakis(Bpin)anthracene 5 was achieved by using a combination of [Ir(OMe)(COD)]2 and tmphen as the catalyst. Compound 5 was
5-Azadibenzo[a,g]corannulene
5-Azadibenzo[a,g]corannulene, the first azacorannulene with a nitrogen on the rim, has been synthesized in seven steps from 4-bromoisoquinoline. The strained pyridine ring opens thermally to a
Iridium-catalyzed direct tetraborylation of perylene bisimides.
TLDR
Oxidation of tetraborylated PBI with hydroxylamine hydrochloride affords tetrahydroxy PBI in excellent yield, which exhibits a substantially blue-shifted absorption spectrum due to an intramolecular hydrogenbonding interaction between carbonyl and hydroxy groups.
...
...