Sterically Crowded Trianglimines—Synthesis, Structure, Solid‐State Self‐Assembly, and Unexpected Chiroptical Properties

Prusinowska, Natalia; Bardziński, Mateusz; Janiak, Agnieszka; Skowronek, Paweł; Kwit, Marcin

doi:10.1002/asia.201800938

“…Synthesis following a recently published protocol for the double bromination of terephthalaldehyde. 21 The crude product was purified by crystallization from chloroform to afford white needles of compound 1 in a yield of 57% (9.91 g, 33.9 mmol). 1…”

Section: Methodsmentioning

confidence: 99%

Double Ring-Closing Approach for the Synthesis of 2,3,6,7-Substituted Anthracene Derivatives

Meindl

¹

,

Pfennigbauer

²

,

Stöger

³

et al. 2020

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Anthracene derivatives have been used for a wide range of applications and many different synthetic methods for their preparation have been developed. However, despite continued synthetic efforts, introducing substituents in some positions has remained difficult. Here we present a method for the synthesis of 2,3,6,7-substituted anthracene derivatives, one of the most challenging anthracene substitution patterns to obtain. The method is exemplified by the preparation of 2,3,6,7-anthracenetetracarbonitrile and employs a newly developed, stable protected 1,2,4,5-benzenetetracarbaldehyde as the precursor. The precursor can be obtained in two scalable synthetic steps from 2,5-dibromoterephthalaldehyde and is converted into the anthracene derivative by a double intermolecular Wittig reaction under very mild conditions followed by a deprotection and intramolecular double ring-closing condensation reaction. Further modification of the precursor is expected to enable the introduction of additional substituents in other positions and may even enable the synthesis of fully substituted anthracene derivatives by the presented approach. File list (3) download file view on ChemRxiv Draft_final.pdf (351.19 KiB) download file view on ChemRxiv SI_final.pdf (550.08 KiB) download file view on ChemRxiv all.cif (559.68 KiB)

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“…Synthesis following a recently published protocol for the double bromination of terephthalaldehyde. 21 The crude product was purified by crystallization from chloroform to afford white needles of compound 1 in a yield of 57% (9.91 g, 33.9 mmol). 1 2,3,6,7-Anthracenetetracarbonitrile TCNA.…”

Section: Methodsmentioning

confidence: 99%

Double Ring-Closing Approach for the Synthesis of 2,3,6,7-Substituted Anthracene Derivatives

Meindl¹,

Pfennigbauer²,

Stöger³

et al. 2020

Preprint

1

0

1

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Anthracene derivatives have been used for a wide range of applications and many different synthetic methods for their preparation have been developed. However, despite continued synthetic efforts, introducing substituents in some positions has remained difficult. Here we present a method for the synthesis of 2,3,6,7-substituted anthracene derivatives, one of the most challenging anthracene substitution patterns to obtain. The method is exemplified by the preparation of 2,3,6,7-anthracenetetracarbonitrile and employs a newly developed, stable protected 1,2,4,5-benzenetetracarbaldehyde as the precursor. The precursor can be obtained in two scalable synthetic steps from 2,5-dibromoterephthalaldehyde and is converted into the anthracene derivative by a double intermolecular Wittig reaction under very mild conditions followed by a deprotection and intramolecular double ring-closing condensation reaction. Further modification of the precursor is expected to enable the introduction of additional substituents in other positions and may even enable the synthesis of fully substituted anthracene derivatives by the presented approach.<br>

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“…The applications of thus obtained polyamines in many various aspects of chemistry were emphasized in a recent review . On the other hand, it is impossible to ignore applications of DACH‐based cyclic polymines in material and supramolecular chemistry and, to a lesser extent, in catalysis and spectroscopy . For instance, Janiak et al.…”

Section: Discussionmentioning

confidence: 99%

One‐Step Construction of the Shape Persistent, Chiral But Symmetrical Polyimine Macrocycles

Kwit

¹

,

Grajewski

²

,

Skowronek

³

et al. 2018

The Chemical Record

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A unique combination of structural flexibility, shape persistency and functionality, makes macrocycles and molecular cages as essential molecular entities that have displayed applications that go beyond chemistry. Among macrocycles, the selectively obtained symmetrical (poly)cyclic polyimines have shown great utility in the design of molecules varied in shape and properties. The reversible and thermodynamically controlled cycloimination reaction is governed by configurational and conformational constraints imposed on the intermediate products, ensures a sufficiently high level of preorganization. The high geometrical control over the macrocycle structure has profound effect on their assembly mode. In this Account, we were interested in showing how the structure of small building blocks affects the structure of macrocyclic product and further, how influenced the association mode of the given macromolecule. The latter is of primarily importance in supramolecular and in material chemistry.

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Sterically Crowded Trianglimines—Synthesis, Structure, Solid‐State Self‐Assembly, and Unexpected Chiroptical Properties

Cited by 19 publications

References 52 publications

Double Ring-Closing Approach for the Synthesis of 2,3,6,7-Substituted Anthracene Derivatives

Double Ring-Closing Approach for the Synthesis of 2,3,6,7-Substituted Anthracene Derivatives

Double Ring-Closing Approach for the Synthesis of 2,3,6,7-Substituted Anthracene Derivatives

One‐Step Construction of the Shape Persistent, Chiral But Symmetrical Polyimine Macrocycles

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