The stereochemistry of compounds 8, 14 and a crystalline derivative of 12 was confirmed by X-ray crystallography, while that of 13 was confirmed by nOe experiments (Supporting Information). In summary we have described and exemplified a new one-pot intramolecular dearomatisation/aza-Michael process that installs a cis-1,2-diaminocyclohexane motif that can be readily further functionalized. The rapid generation of structural and stereochemical complexity from simple achiral precursors reinforces the power of dearomatisation reactions in synthesis. The small polycyclic products have the potential to act as scaffolds for the synthesis of putative bioactive compounds: over 400 compounds based on scaffolds such as 13 have been prepared and contributed to the Public Compound Collection of the Joint European Compound Library within the European Lead Factory project, and results based on our own exploitation of these scaffolds will be reported in due course.