1 Desymmetrisation of aromatic diamines and synthesis of non-symmetrical thiourea derivatives by click-mechanochemistry Vjekoslav Štrukil, a Davor Margetić, a Marina Diana Igrc, a Mirjana Eckert- Maksić* ,a and Tomislav Friščić* ,b a Division of Organic Chemistry and Biochemistry, Ruđer Bošković Institute, Bijenička cesta 54, HR-10002 Zagreb, Croatia; b Department of Chemistry, McGill University, 801 Sherbrooke St., H3A 2K6 Montréal, Québec, Canada Supplementary Material Table of contents Section Page 1. Experimental 2 1.1 General comments 2 1.2 Synthesis of mono-(thio)ureas 1a-e and 3a-b 2 1.3 Synthesis of bis-thioureas 2a-h and 4a-d 6 1.4 Synthesis of urea 2i and mixed urea-thioureas 2j-m 11 2. FTIR spectra 15 3. 1 H and 13 C NMR spectra 18 4. DFT quantum chemical calculations 42 5. Frontier Molecular Orbital (FMO) analysis 47 6. Cartesian coordinates of mono-(thio)ureas 50 Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2012