Studies in Acyl C-H Activation via Aryl and Alkyl to Acyl “Through Space” Migration of Palladium Tanay Kesharwani, Akhilesh K. Verma, Daniel Emrich, Jeffrey A. Ward, Richard C. Larock* † Department of Chemistry, Iowa State University, Ames IA, 50011 larock@iastate.edu Table of Contents Pages General S2-S2 General procedure for the preparation of 1 and 1-d S2-S3 General procedure for the synthesis of nitriles used for the preparation of aldehydes 9, 11, 13, 14 and 20 S3-S5 Preparation of the nitrile for synthesis of 1-(2-iodophenyl)cyclobutanecarboxaldehyde S5-S6 Preparation of 2-(2-iodophenyl)-2,3-dihydro-1H-indene-2-carbonitrile S6-S7 General procedure for the preparation of aldehydes 9, 11, 13, 14, 16, 18 and 20 S7-S10 Preparation of 8-iodo-1-naphthaldehyde (22) S10-S10 Preparation of (chloromercurio)acetaldehyde (26) S10-S11 General procedure for the migration/nucleophilic trapping reaction S11-S12 General procedure for the migration/decarbonylation reaction S12-S13 Preparation of methyl 1-naphthoate (24) S13-S14 General procedure for the preparation of 29 and 29D S14-S15 Preparation of exo-2-(bicyclo[2.2.1]hept-2-yl)-1-exo-(3- chloropalladiobicyclo[2.2.1]hept-2-yl)ethanone (30) S15-S15 Carbonylation of 30 to form methyl exo-3-(2-bicyclo[2.2.1]hept-2-yl)acetyl)-exo- bicyclo[2.2.1]heptane-2-carboxylate (31) S15-S16 Preparation of exo-3-[2-(3-deuterobicyclo[2.2.1]hept-2-yl)acetyl]-exo- bicyclo[2.2.1]heptane-2-carboxylate (31D) S16-S16 General procedure for the preparation of 32 and 32D S16-S17 References S18-S18 1 H and 13 C NMR spectra S19-S56 1 S