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Oxidative Photocyclization

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Helicene Chemistry

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Abstract

Oxidative photocyclization is the most widely used method to the synthesis of carbohelicenes, in particular the long carbohelicenes. It is also an efficient way to the synthesis of heterohelicenes including azahelicenes and thiahelicenes. In this chapter, we first introduce the synthesis of various carbohelicenes by different oxidative photocyclization strategy starting from the stilbene precursors. With two aryl groups in the stilbene precursors bearing heteroaromatic rings, azahelicenes and thiahelicenes can be regioselectively synthesized by the similar oxidative photocyclization. Based on this methodology, optically active helicenes can also be obtained after resolution, which makes these molecules applicable. Although this methodology has been widely utilized, it is difficult to be used for large-scale preparation because the photocyclization needs highly diluted solution (usually ca. 10−3 M) to prevent the [2+2] intermolecular cycloaddition. Recently, chemists found a solution—the continuous flow strategy—to solve the problem of large-scale preparation. Under the optimal condition, the helicene can be prepared at the rate of 60 mg/h.

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  1. Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing, China

    Chuan-Feng Chen & Yun Shen

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Chen, CF., Shen, Y. (2017). Oxidative Photocyclization. In: Helicene Chemistry. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-662-53168-6_3

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