S1 Dehydrogenative Transformations of Imines Using a Heterogeneous Photocatalyst Colby M. Adolph, Jacob Werth, Ramajeyam Selvaraj, Evan C. Wegener, and Christopher Uyeda* Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, United States Correspondence: cuyeda@purdue.edu 1. Acid Screen and Catalyst Recycling Experiment S2 2. Cyclic Voltammetry Data for N-Benzyltryptamine S3 3. XRD Data for the Pt/TiO 2 Photocatalyst S4 4. A Proposed Mechanism for the Formation of 25 S5 5. NMR Spectra for Products S6 6. IR Spectra for Products S33
S2 1. Acid Screen and Catalyst Recycling Experiment Acid Screen A screen of acid additives was conducted under the standard conditions shown in Table 1. Table S1. Screen of Acid Additives. entry Acid (2.0 equiv) Conversion (%) 1 PhCO 2 H >99 81 2 F 3 CCO 2 H >99 87 3 HCO 2 H 97 77 4 ptsoh 14 0 5 H 2 SO 4 (aq) 12 0 6 TMSCl 9 0 Yield 2 (%) Catalyst Recycling Experiment A 50 ml Schlenk tube was charged with a magnetic stir bar, the tryptamine substrate 1 (0.2 mmol), the Pt/TiO 2 catalyst (5 mg), AcOH (0.4 mmol), and MeOH (3.0 ml). The reaction vessel was sealed and degassed by the freeze pump thaw procedure. Reactions were stirred under irradiation by a 100 W Hg lamp (UVP Blak Ray B 100YP). After 15 h, the reaction mixture was quenched with aqueous sodium hydroxide (1.0 M, 10 ml), and the product was extracted using CH 2 Cl 2 (3 x 5 ml). The aqueous phase containing suspended Pt/TiO 2 was centrifuged, and the solution was decanted from the solid pellet. The solid pellet was washed twice with distilled water and dried overnight in an oven set at 200 C yielding 84% of the mass of the original catalyst. The recycled catalyst was reused in a standard catalytic reaction using substrate 1, providing 2 in 87% yield.
S3 2. Cyclic Voltammetry Data for N-Benzyltryptamine Cyclic voltammograms were acquired using a glassy carbon working electrode (3 mm diameter disk) under an atmosphere of N 2 (scan rate = 100 mv/s). The potentials were internally referenced to the reversible Cp 2 Fe/Cp 2 Fe + couple. 4x10-6 Current (A) 2x10-6 0-2x10-6 -0.8-0.6-0.4-0.2 0.0 0.2 0.4 0.6 0.8 1.0 Potential (V vs. Fc/Fc + ) Figure S1. Cyclic voltammogram for Cp 2 Fe in MeOH. 6x10-6 4x10-6 Current (A) 2x10-6 0-2x10-6 -0.8-0.6-0.4-0.2 0.0 0.2 0.4 0.6 0.8 1.0 Potential (V vs. Fc/Fc + ) Figure S2. Cyclic voltammogram for N benzyltryptamine (1) and Cp 2 Fe in MeOH.
Supporting Information S4 S 3. XRD Data for the Pt/TiO2 Photocatalyst Figure S3. Powder XRD pattern for the Pt/TiO 2 catalyst showing the expected signals for anatase and rutile TiO 2.
S5 4. A Proposed Mechanism for the Formation of 25 Figure S4. Proposed mechanism for the formation of 25.
S6 5. NMR Spectra for Products Figure S5. 1 H NMR spectrum for 2. Figure S6. 13 C{ 1 H} NMR spectrum for 2.
S7 Figure S7. 1 H NMR spectrum for 4. Figure S8. 13 C{ 1 H} NMR spectrum for 4.
S8 Figure S9. 1 H NMR spectrum for 5. Figure S10. 13 C{ 1 H} NMR spectrum for 5.
S9 Figure S11. 1 H NMR spectrum for 6. Figure S12. 13 C{ 1 H} NMR spectrum for 6.
S10 N N H N Figure S13. 1 H NMR spectrum for 7. Figure S14. 13 C{ 1 H} NMR spectrum for 7.
S11 Figure S15. 1 H NMR spectrum for 8. Figure S16. 13 C{ 1 H} NMR spectrum for 8.
S12 Figure S17. 1 H NMR spectrum for 9. Figure S18. 13 C{ 1 H} NMR spectrum for 9.
S13 Figure S19. 19 F NMR spectrum for 9.
S14 Figure S20. 1 H NMR spectrum for 10. Figure S21. 13 C{ 1 H} NMR spectrum for 10.
S15 N N H OH Figure S22. 1 H NMR spectrum for 11. Figure S23. 13 C{ 1 H} NMR spectrum for 11.
S16 Figure S24. 1 H NMR spectrum for 12. Figure S25. 13 C{ 1 H} NMR spectrum for 12.
S17 Figure S26. 1 H NMR spectrum for 13. Figure S27. 13 C{ 1 H} NMR spectrum for 13.
S18 Figure S28. 19 F NMR spectrum for 13.
S19 Figure S29. 1 H NMR spectrum for 14. Figure S30. 13 C{ 1 H} NMR spectrum for 14.
S20 Figure S31. 1 H NMR spectrum for 15. Figure S32. 13 C{ 1 H} NMR spectrum for 15.
S21 Figure S33. 19 F NMR spectrum for 15.
S22 Figure S34. 1 H NMR spectrum for 16. Figure S35. 13 C{ 1 H} NMR spectrum for 16.
S23 Figure S36. 1 H NMR spectrum for 17. Figure S37. 13 C{ 1 H} NMR spectrum for 17.
S24 Figure S38. 1 H NMR spectrum for 18.
S25 Figure S39. 1 H NMR spectrum for 19. Figure S40. 13 C{ 1 H} NMR spectrum for 19.
S26 Figure S41. 1 H NMR spectrum for 20. Figure S42. 13 C{ 1 H} NMR spectrum for 20.
S27 Figure S43. 19 F NMR spectrum for 20.
S28 Figure S44. 1 H NMR spectrum for 21. Figure S45. 13 C{ 1 H} NMR spectrum for 21.
S29 Figure S46. 1 H NMR spectrum for 22. Figure S47. 13 C{ 1 H} NMR spectrum for 22.
S30 Figure S48. 1 H NMR spectrum for 23. Figure S49. 13 C{ 1 H} NMR spectrum for 23.
S31 Figure S50. 1 H NMR spectrum for 24. Figure S51. 13 C{ 1 H} NMR spectrum for 24.
S32 Figure S52. 1 H NMR spectrum for 25. Figure S53. 13 C{ 1 H} NMR spectrum for 25.
Supporting Information S33 6. IR Spectra for Products N F N H F F F F Figure S54. IR spectrum for 9.
Supporting Information S34 N N H OH Figure S55. IR spectrum for 11.
Supporting Information S35 N N Cl Figure S56. IR spectrum for 12.
Supporting Information S36 N N H CF 3 Figure S57. IR spectrum for 13.
Supporting Information S37 N F N H Figure S58. IR spectrum for 15.
Supporting Information S38 N N H Figure S59. IR spectrum for 16.