Dehydrogenative Transformations of Imines Using a Heterogeneous Photocatalyst. Supporting Information

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1 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

2 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 > F 3 CCO 2 H > HCO 2 H ptsoh H 2 SO 4 (aq) 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.

3 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) 2x x Potential (V vs. Fc/Fc + ) Figure S1. Cyclic voltammogram for Cp 2 Fe in MeOH. 6x10-6 4x10-6 Current (A) 2x x Potential (V vs. Fc/Fc + ) Figure S2. Cyclic voltammogram for N benzyltryptamine (1) and Cp 2 Fe in MeOH.

4 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.

5 S5 4. A Proposed Mechanism for the Formation of 25 Figure S4. Proposed mechanism for the formation of 25.

6 S6 5. NMR Spectra for Products Figure S5. 1 H NMR spectrum for 2. Figure S6. 13 C{ 1 H} NMR spectrum for 2.

7 S7 Figure S7. 1 H NMR spectrum for 4. Figure S8. 13 C{ 1 H} NMR spectrum for 4.

8 S8 Figure S9. 1 H NMR spectrum for 5. Figure S C{ 1 H} NMR spectrum for 5.

9 S9 Figure S11. 1 H NMR spectrum for 6. Figure S C{ 1 H} NMR spectrum for 6.

10 S10 N N H N Figure S13. 1 H NMR spectrum for 7. Figure S C{ 1 H} NMR spectrum for 7.

11 S11 Figure S15. 1 H NMR spectrum for 8. Figure S C{ 1 H} NMR spectrum for 8.

12 S12 Figure S17. 1 H NMR spectrum for 9. Figure S C{ 1 H} NMR spectrum for 9.

13 S13 Figure S F NMR spectrum for 9.

14 S14 Figure S20. 1 H NMR spectrum for 10. Figure S C{ 1 H} NMR spectrum for 10.

15 S15 N N H OH Figure S22. 1 H NMR spectrum for 11. Figure S C{ 1 H} NMR spectrum for 11.

16 S16 Figure S24. 1 H NMR spectrum for 12. Figure S C{ 1 H} NMR spectrum for 12.

17 S17 Figure S26. 1 H NMR spectrum for 13. Figure S C{ 1 H} NMR spectrum for 13.

18 S18 Figure S F NMR spectrum for 13.

19 S19 Figure S29. 1 H NMR spectrum for 14. Figure S C{ 1 H} NMR spectrum for 14.

20 S20 Figure S31. 1 H NMR spectrum for 15. Figure S C{ 1 H} NMR spectrum for 15.

21 S21 Figure S F NMR spectrum for 15.

22 S22 Figure S34. 1 H NMR spectrum for 16. Figure S C{ 1 H} NMR spectrum for 16.

23 S23 Figure S36. 1 H NMR spectrum for 17. Figure S C{ 1 H} NMR spectrum for 17.

24 S24 Figure S38. 1 H NMR spectrum for 18.

25 S25 Figure S39. 1 H NMR spectrum for 19. Figure S C{ 1 H} NMR spectrum for 19.

26 S26 Figure S41. 1 H NMR spectrum for 20. Figure S C{ 1 H} NMR spectrum for 20.

27 S27 Figure S F NMR spectrum for 20.

28 S28 Figure S44. 1 H NMR spectrum for 21. Figure S C{ 1 H} NMR spectrum for 21.

29 S29 Figure S46. 1 H NMR spectrum for 22. Figure S C{ 1 H} NMR spectrum for 22.

30 S30 Figure S48. 1 H NMR spectrum for 23. Figure S C{ 1 H} NMR spectrum for 23.

31 S31 Figure S50. 1 H NMR spectrum for 24. Figure S C{ 1 H} NMR spectrum for 24.

32 S32 Figure S52. 1 H NMR spectrum for 25. Figure S C{ 1 H} NMR spectrum for 25.

33 Supporting Information S33 6. IR Spectra for Products N F N H F F F F Figure S54. IR spectrum for 9.

34 Supporting Information S34 N N H OH Figure S55. IR spectrum for 11.

35 Supporting Information S35 N N Cl Figure S56. IR spectrum for 12.

36 Supporting Information S36 N N H CF 3 Figure S57. IR spectrum for 13.

37 Supporting Information S37 N F N H Figure S58. IR spectrum for 15.

38 Supporting Information S38 N N H Figure S59. IR spectrum for 16.

CHEM254 #4 The Synthesis of a Tertiary Alcohol Using a Pre-Made Grignard Reagent 1

CHEM254 #4 The Synthesis of a Tertiary Alcohol Using a Pre-Made Grignard Reagent 1 Background In this project, we will perform a Grignard reaction using a pre-made Grignard reagent. Grignard reagents can