Nature Chemistry
Nature Chemistry
5 years ago

Organocatalytic stereoselective [8+2] and [6+4] cycloadditions

Organocatalytic stereoselective [8+2] and [6+4] cycloadditions
Rasmus Mose, Jesper Larsen, Karl Anker Jørgensen, Gert Preegel, Sofie Jakobsen, Eva Høgh Iversen
Cycloadditions that involve more than six π electrons are termed higher-order cycloadditions and are an excellent tool for solving complex synthetic challenges, as they provide direct access to polycyclic scaffolds that contain medium-sized rings. They have interesting synthetic potential for the discovery of new bioactive molecules and in natural product synthesis. It is peculiar that stereocontrolled [8+2] and [6+4] cycloadditions have been largely neglected for the past 50 years. Here we demonstrate a cross-dienamine activation of 2-cyclopentenone and the unprecedented endocyclic linear-dienamine activation of 2-cyclohexenones and 2-cycloheptenones. These dienamine intermediates undergo aminocatalytic stereoselective [8+2], [6+4] and formal [4+2] cycloadditions with various heptafulvenes. The periselectivities of the cycloadditions are controlled based on the ring size of the 2-cycloalkenones and the substitution patterns of the heptafulvenes. The chiral products obtained undergo various chemical and photochemical single-step transformations that give access to other classes of all-carbon polycyclic scaffolds.

Publisher URL: http://dx.doi.org/10.1038/nchem.2682

DOI: 10.1038/nchem.2682

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