Chemical and Photochemical Synthesis of Thiophene-based Helicenes

doi:10.7517/j.issn.1674-0475.2017.04.021

Abstract

Abstract:

In this review, the main progresses on the chemical and photochemical synthesis of thiophene-based helicenes are described. In the section of chemical method for synthesis of helicenes, based on ditheinothiophene (DTT) as building blocks, the single helicenes are normally designed and synthesized to make bi-DTT as precursor first, and then implement sulfur substituted cyclization for target helicenes. However, it may not be successful for making longer and longer helicenes due to the increasing intramolecular interactions between the two moieties of precursor molecule. By the synthetic strategy of increasing the solubilizing groups in making helicenes, the target molecular structures can be changed from single helicenes to double helicenes. In the section of photochemical synthesis of helicenes, the oxidative photocyclization is confirmed to be an effective method for preparation of helicenes. Due to the double radical mechanism in the photochemistry of double bond under irradiation, the cyclization step gives the effective target products including both racemate and mesomer at the same time. In addition, the prospects for the field of thiophene-based helicenes are put forward in three aspects:1) design the new isomers of helicenes based on the position isomerism of sulfur atoms in the terminal thiophene rings of helicene; 2) design and synthesis of double or multiple helicenes with new structures; 3) find the application of helicene enantiomers in asymmetric catalysis, chiral assembly and so on.

Key words: thiophene-based helicene, double helicene, chemical synthesis, photochemical synthesis, crystal structure

WANG Hua. Chemical and Photochemical Synthesis of Thiophene-based Helicenes[J]. Imaging Science and Photochemistry, 2017, 35(5): 603-613.

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