To circumvent the unselective enolate alkylation, cyclopropanation of the diastereomeric enoxysilanes and regioselective opening was pursued (Scheme 9). Simmons-Smith cyclopropanation 57 of 9-5 proceeded with high diastereoselectivity (>20:1 dr). In situ deprotection of the intermediate siloxycyclopropane with TBAT provided cyclopropanol in 75% combined yield as a mixture of C5-epimers, and in 31% isolated yield as the single desired diastereomer 9-7. The use of Ziese's dimer, [PtCl2(C2H4)]2, 58 initiated a regioselective opening of cyclopropanol 9-7 to form xylogranatopyridine B (1-1) in 69% yield. Remarkably, this protocol avoided the facile epimerization of the highly acidic methyl ketone in 1-1, which was the central challenge with the a-methylation approach. Careful Scheme 8. Reaction Conditions Optimization of the Liebeskind Pyridine Synthesis a Yield of the crude reaction mixture on 0.1 mmol scale, was determined by 1 H NMR using 1,3,5-trimethoxybenzene as an internal standard. b 2.0 equiv Et3N was utilized instead of quinuclidine. examination of the reaction of 9-7 with Ziese's dimer showed a minor side product was produced in 4% yield, which was characterized as the exocyclic enone 9-8. This enone side product (9-8) may arise from initial isomerization of the cyclopropane to the allylic alcohol, and subsequent aerobic oxidation to the enone.