Theoretical Investigation of the Photochemical C 2 –C 6 Cyclisation of Enyne–Heteroallenes

Herein we discuss computations that explain experimental results regarding a highly efficient triplet analogue of the C 2 –C 6 cyclisation of enyne–heteroallenes recently discovered by Schmittel and co‐workers.1 To shed some light on the reasons for the differences found between enyne–carbodiimides, enyne–ketenimines and enyne–allenes, we have computed the reaction profiles of the C 2 –C 6 and of the C 2 –C 7 cyclisations for various model compounds, assuming that the reactions take place on the lowest‐lying triplet surfaces. Our results nicely explain the differences and the unexpected high efficiency found for the enyne–carbodiimides. The differences between enyne–carbodiimides and enyne–ketenimines prove to be due to differences in the shapes of the corresponding triplet surfaces. In contrast to the enyne–carbodiimides, for which our calculations predict that a direct cyclisation to the biradical intermediates should occur after the vertical excitation, the enyne–ketenimines relax into a local minimum on the triplet surface. As a consequence, further reaction channels are opened. Our computations indicate that enyne–allene compounds do not react because the necessary excitation energy lies outside the range of the employed triplet photosensitizer. Finally, the close agreement between our results and the experimental findings indicates that the underlying reasons for the differences in the photochemical behaviour of enyne–carbodiimides, enyne–ketenimines and enyne–allenes are related to differences in the electronic structures of the parent systems, while substituent effects are less important.