Electronic Supplementary Material (ESI) for Green Chemistry. This journal is © The Royal Society of Chemistry 2018 Electronic Supporting Information Valorization of 2,5-Furandicarboxylic Acid. Diels-Alder Reactions with Benzyne Eric M. Serum, Sermadurai Selvakumar, Nicholas Zimmermann, and Mukund P. Sibi* Department of Chemistry and Biochemistry, North Dakota State University, Fargo, North Dakota, USA, E-mail:
[email protected] S 1 Table of Contents Section Heading Page 1 General Methods S 3 2 Equations 1–4 Discussion of Metrics S 3 3 Synthesis of Dimethyl-2,5-furandicarboxylate 5 S 4 4 Synthesis 2,5-Diformylfuran 2A S 5 5 Synthesis (2E,2'E)-3,3'-(furan-2,5-diyl)diacrylic acid 3 S6 6 Synthesis Dimethyl 3,3'-(furan-2,5-diyl)(2E,2'E)-diacrylate 13 S 7 7 Synthesis Dimethyl 3,3'-(furan-2,5-diyl)dipropionate 14 S 8 8 Diene 15 (2,5-dimethylfuran) S 9 9 Diels Alder Reactions Table S 1 Desilylation of 16: Exploring the Relationship Between S 10 Temperature and Benzyne Trapping by Furan Diene Substrates Table S 2 Thermolysis of 19 generated in situ: Trapping in Chloroform S 12 Table S 3 Partially Isolated 19 Thermolysis: Preliminary Trapping and S 13 Substrate Screening Table S 4 Partially Isolated 19 Thermolysis: Substrate Screen Exploring the S 15 Relationship Between Stoichiometry and Reaction Outcome Reaction Diene 13 with Benzyne Generated by Thermolysis Fig. S 1 S 16 Table S 5 Partially Isolated 19 Thermolysis and Trapping Single Shot: S 17 Method and Substrate Screening While Limiting Availability of Nitrite Table S 6 Crude Preparation of 19 Added Directly to Diene Solution S 18 10 Identification Dimethyl 3,4-epoxy-7-oxabenzonorbornadiene-1,4- S 19 dicarboxylate 11 Hydrolysis 7-Oxabenzonorbornadiene-1,4-dicarboxylic acid S 20 12 Deoxyaromatization Table S 7 Naphthalenes from 7-Oxabenzonorbornadienes: Trimethylsilyl S 21 Iodide Mediated Deoxyaromatization 13 Catalytic Hydrogenation S 23 14 Dehydroaromatizations S 25 Table S 9 Naphthalenes by Dehydro-aromatization of 7- S 25 Oxabenzonorbornenes.