Abstract
With the development of synthetic protocols, the application of helicenes in asymmetric catalysis has attracted more attentions. So far, dozens of helicene-based catalysts have been reported, and they are summarized in this chapter in terms of functionalities of helicenes. First, the non-functionalized helicenes can be utilized as an asymmetric trigger for the autocatalytic addition reactions. Both the macrocyclic amide based on [4]helicene and bihelicenyls can catalyze the addition of diethylzinc to aldehyde in moderate to good enantioselectivity. Optically pure (P)-1-aza[6]helicene and (M)-2-aza[6]helicene can be used as the catalyst in the kinetic resolution of alcohol. N-oxides of 1-aza[6]helicene are good catalysts for the asymmetric ring-opening of epoxides, and also show high efficiency for the asymmetric propargylation of aldehyde. The protonated 2-amino-1-aza[1]helicenes are excellent dual hydrogen bonding donor catalysts for the asymmetric addition reaction between dihydroindole and nitroalkene, and also for the asymmetric Diels-Alder reaction of nitroalkene with dienes. Helicenes with phosphorus functionality can be used for the asymmetric hydrogenation of itaconate, the kinetic resolution of vinyl alcohol ester, Rh-catalyzed asymmetric hydroformylation and Ir-catalyzed asymmetric allylic amination. Moreover, a series of phosphole-embedded helicene ligands were also developed, which can be used as gold catalysis and HelPhos organocatalysts for the cyclization of N-tethered enynes, asymmetric [2+2] cycloaddition of allenenes and [2+4] cycloaddition of allene-dienes in good enantioselectivity. Phosphahelicenes can also be utilized as organocatalyst for the [3+2] cycloaddition between the allene and electron-poor alkenes with excellent diastereoselectivity and enantioselectivity.
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Chen, CF., Shen, Y. (2017). Helicenes in Catalysis. In: Helicene Chemistry. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-662-53168-6_9
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DOI: https://doi.org/10.1007/978-3-662-53168-6_9
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