Sequential [6+2], [2+2], and [3+2] annulations for rapid assembly of multiple fragmentsElectronic supplementary information (ESI) available: Experimental procedure, spectral data, and Fig. S1-S25. CCDC 910960 and 910961. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c2cc38854e

Assembly of four components through sequential [6+2], [2+2], and [3+2] annulations on an azulenone manifold allows for five-step access to a natural product-inspired scaffold with exquisite control of the ten consecutive stereocenters. X-ray analysis was used to define the spatial arrangement of the three fragments and functional groups on this rigid scaffold. Stereo-controlled assembly of four components on an azulenone manifold allows five-step access to a natural product-inspired scaffold for fragment-based drug design.