A series of diverse aromatic azadienetriyne and azatriynes was synthesised. These compounds were subjected to transition metal-mediated [2+2+2] cycloisomerisation to form pentacyclic or hexacyclic helically chiral azahelicene or azahelicene-like structures mostly in moderate yields. Introducing stereogenic centre(s) into selected azatriynes, cyclisation proceeded in a stereoselective fashion providing aza[5]helicenes or aza[6]helicene-like compounds in up to a 100:0 diastereomeric ratio. Gibbs energy differences between corresponding pairs of diastereomers (calculated at the DFT(B3LYP)/TZV+P level) were in good agreement with the experimental data and allowed for the prediction of the stereochemical outcome of the reaction. This study presents for the first time asymmetric synthesis of azahelicene derivatives in high optical purities.

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