With the stannane fragment in hand, the Stille coupling with vinyl triflate 3-5 was explored. The attempted cross-coupling with Corey's conditions utilizing Pd(PPh3)4, CuCl, and LiCl resulted only in proto-destannylation and decomposition of 3-5. Furthermore, modification of ligands, copper salts, or other additives employed did not lead to the desired coupling product. Additionally, it was found that the neat triflate rapidly decomposed under ambient conditions. In order to attenuate these undesired pathways and obtain 5-1, we attempted to switch the polarity of the coupling partners. However, conversion of the β-triflate to the β-stannyl enone by Pd-catalyzed conditions or nucleophilic addition of a stannyl metal-species was unsuccessful (not shown). Due to the difficulty of realizing the tetracyclic core of xylogranatopyridine B (1-1) by a Stille cross-coupling approach, we explored alternative pyridine synthesis strategies.