Synthesis of the Stolz cross-coupling precursors, significance of solvent choice for hydrogenolysis of carbamate 9, optimization of the synthesis of 6,7-spiroacetal 20, synthesis of 7,6-spiroacetal 24 and attempted synthesis of larger ring systems, synthesis of spiroacetals 59 and 60, general experimental details, experimental procedures and complete compound characterization data, 1 H-and 13 C-NMR data for all compounds, X-ray crystallographic data for spiroacetals 8 and 24, library enumeration including KNIME workflows, library analysis and selection of diversity subset for physical library synthesis. This material is available free of charge via the Internet at