Supporting Information For Calcium-Catalyzed Formal [5+2] Cycloadditions of Alkylidene b-Ketoesters with Olefins: Chemodivergent Synthesis of Highly Functionalized Cyclohepta[b]indole Derivatives Ariel N. Parker, M. Cynthia Martin, Raynold Shenje, and Stefan France* School of Chemistry and Biochemistry, Georgia Institute of Technology, 901 Atlantic Drive, Atlanta, Georgia 30332 stefan.france@chemistry.gatech.edu Table of Contents 1. General Methods 2. Experimental Procedures A. Reaction Optimization Tables for Cyclohepta[b]indoles B. Synthesis of b-Keto Esters C. Synthesis of Alkylidenes D. Synthesis of Alkene 3b E. Synthesis of Cyclohepta[b]indoles F. Olefins that Failed G. Synthesis of Krapcho Decarboxylated Cyclohepta[b]indoles H. Reaction Optimization Table for Bicyclic System (Phenyl-Vinyl (thio)ethers) I. Derivatization 3. References 4. Copies of NMR Spectra 5. Crystal Data for Compound 6ap (AP-Xray-01) 1. General Methods Chromatographic purification was performed as flash chromatography with Silicycle SiliaFlash P60 silica gel (40-63µm) or preparative thin-layer chromatography (prep-TLC) using silica gel F254 (1000 µm) plates and solvents indicated as eluent with 0.1-0.5 bar pressure. For quantitative flash chromatography, technical grades solvents were utilized. Analytical thin-layer chromatography (TLC) was performed on Silicycle SiliaPlate TLC silica gel F254 (250 µm) TLC glass plates. Visualization was accomplished with UV light. Infrared (IR) spectra were obtained via attenuated total reflection (ATR) with a diamond plate using a Bruker ALPHA Fourier-transform infrared spectrophotometer. The IR bands are characterized as broad (br), weak (w), medium (m), and strong (s). Proton and carbon nuclear magnetic resonance spectra ( 1 H NMR and 13 C NMR) were recorded on a Varian Mercury Vx 300 MHz spectrometer or a Bruker 500 MHz spectrometer with solvent resonances as the internal standard ( 1 H NMR: CDCl 3 at 7.26 ppm or DMSO-d 6 at 2.50; 13 C NMR: CDCl 3 at 77.0 ppm or DMSO-d 6 at 39.5). 1 H NMR data are reported as follows: chemical S-1