Supporting Information

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1 Supporting Information 4-Hydroxyphenacyl Ammonium Salts: A Photoremovable Protecting Group for Amines in Aqueous Solutions Iwona Bownik, Peter Šebej,, Jaromír Literák*,, Dominik Heger,, Zdeněk Šimek, Richard S. Givens, Petr Klán*,, Department of Chemistry, Masaryk University, Kamenice 5, , Brno, Czech Republic. RECETOX, Faculty of Science, Masaryk University, Kamenice 5, , Brno, Czech Republic. Department of Chemistry, University of Kansas, 1251 Wescoe Hall Drive, Malott Hall, Lawrence, Kansas 66045, United States * literak@chemi.muni.cz; Phone: ; Fax: ; klan@sci.muni.cz; Phone: ; Fax: Contents Titration Data Preparative Irradiation Data NMR Spectra UV Spectrum of 1f Output spectrum of a medium-pressure Hg lamp S2 S3 S4 S5 S6 S26 S27 S28 S1

2 Figure S1. The ph Dependence of the Absorption Spectra of 1a in Aqueous Buffers (see the main text for details) Table S1. The molar absorption coefficients of the A and B forms in 1a c a compound ε (A form) ε (B form) 1a b c a Molar absorption coefficients (mol dm 3 cm 1 ) were obtained using a UV titration method from the deconvoluted spectra (see Figure 1 and the Experimental Part in the main text). S2

3 Figure S2. Titration of 1a using NMR: the ph dependence of 1 H NMR chemical shifts measured for the OH group. The buffered (phosphate, c = 62.4 mmol dm 3 ) aqueous solution of 1a (~ mol dm 3 ) was titrated in the ph range of with the solution of NaOD in D 2 O. Figure S3. Titration of 1a using NMR: the ph dependence of 1 H NMR chemical shifts measured for the NH group. The buffered (phosphate, c = 62.4 mmol dm 3 ) aqueous solution of 1a (~ mol dm 3 ) was titrated in the ph range of with the solution of NaOD in D 2 O. S3

4 Figure S4. Preparative irradiation of 1a (c = 7 mmol dm 3 ) at ph = 4.0 and λ irr = 313 nm: the dependence of the product yields on the conversion of 1a. The formate buffer composition: HCOONa (c = mol dm 3 ) was titrated with a DCl solution in D 2 O. The yields were determined by 1 H NMR (sodium 3-(trimethylsilyl)-2,2,3,3-tetradeuteropropionate was used as an internal standard). Figure S5. Preparative irradiation of 1a (c = 7 mmol dm 3 ) at ph = 4.0 and λ irr = 313 nm: the dependence of the product yields on the conversion of 1a. The acetate buffer composition: CH 3 COONa (c = mol dm 3 ) titrated with a DCl solution in D 2 O. The yields were determined by 1 H NMR (sodium 3-(trimethylsilyl)-2,2,3,3-tetradeuteropropionate was used as an internal standard). S4

5 Figure S6. Preparative irradiation of 1a (c = 7 mmol dm 3 ) at ph = 4.0 and λ irr = 313 nm: the dependence of the product yields on the conversion of 1a. The phosphate buffer composition: Na 3 PO 4 (c = mol dm 3 ) titrated with a DCl solution in D 2 O. The yields were obtained by 1 H NMR (sodium 3-(trimethylsilyl)-2,2,3,3-tetradeuteropropionate was used as an internal standard). Figure S7. Preparative irradiation of 1a (c = 7 mmol dm 3 ) at ph = 4.0 and λ irr = 313 nm: the dependence of the product yields on the conversion of 1a. The acetate buffer composition: CH 3 COONa (c = mol dm 3 ) titrated with a DCl solution in D 2 O. The yields were obtained by 1 H NMR (sodium 3-(trimethylsilyl)-2,2,3,3-tetradeuteropropionate was used as an internal standard). S5

6 Figure S8. 1 H NMR (CD 3 OD, 500 MHz): 2-(Diethylamino)-1-(4-hydroxyphenyl)ethanone hydrochloride (1a) f1 (ppm) S6

7 Figure S9. 13 C { 1 H} NMR (CD 3 OD, 126 MHz): 2-(Diethylamino)-1-(4-hydroxyphenyl)ethanone hydrochloride (1a) f1 (ppm) S7

8 Figure S10. 1 H NMR (CD3OD, 500 MHz): 1-(4-Hydroxyphenyl)-2-(piperidin-1-yl)ethanone hydrobromide (1b) S8

9 Figure S C { 1 H} NMR (CD 3 OD, 126 MHz): 1-(4-Hydroxyphenyl)-2-(piperidin-1-yl)ethanone hydrobromide (1b) f1 (ppm) S9

10 Figure S12. 1 H NMR (CD 3 OD, 500 MHz): 2-Amino-1-(4-hydroxyphenyl)ethanone hydrochloride (1c) f1 (ppm) S10

11 Figure S C { 1 H} NMR (CD 3 OD, 126 MHz): 2-Amino-1-(4-hydroxyphenyl)ethanone hydrochloride (1c) S11

12 Figure S14. 1 H NMR (CD 3 OD, 500 MHz): Methyl ester of N-[2-(4-hydroxyphenyl)-2-oxoethyl]glycine hydrochloride (1d) S12

13 Figure S C { 1 H} NMR (CD 3 OD, 126 MHz): Methyl ester of N-[2-(4-hydroxyphenyl)-2-oxoethyl]glycine hydrochloride (1d) f1 (ppm) S13

14 Figure S16. 1 H NMR (DMSO-d 6, 500 MHz): Methyl ester of N-[2-(4-hydroxyphenacyl)-2-oxoethyl]phenylalanine hydrochloride (1e). S14

15 Figure S C { 1 H} NMR (DMSO-d 6, 126 MHz): Methyl ester of N-[2-(4-hydroxyphenacyl)-2-oxoethyl]phenylalanine hydrochloride (1e). S15

16 Figure S18. 1 H NMR (CDCl 3, 500 MHz): 1-(4-(benzyloxy)phenyl)-2-bromoethanone (4) S16

17 Figure S C { 1 H} NMR (DMSO-d 6, 126 MHz): 1-(4-(benzyloxy)phenyl)-2-bromoethanone (4) S17

18 Figure S20. 1 H NMR (DMSO-d 6, 500 MHz): 2-(4-benzyloxyphenyl)-N,N,N-triethyl-2-oxoethanaminium bromide (5) S18

19 Figure S C { 1 H} NMR (DMSO-d 6, 126 MHz): 2-(4-benzyloxyphenyl)-N,N,N-triethyl-2-oxoethanaminium bromide (5) S19

20 9.22 Figure S22. 1 H NMR (DMSO-d6, 500 MHz): triethyl[2-(4-hydroxyphenyl)-2-oxoethyl]amonium bromide (1f) S20

21 Figure S C { 1 H} NMR (DMSO-d 6, 126 MHz): triethyl[2-(4-hydroxyphenyl)-2-oxoethyl]amonium bromide (1f) f1 (ppm) S21

22 Figure S24. 1 H 15 N HMBC NMR (DMSO-d 6, 500 MHz): triethyl[2-(4-hydroxyphenyl)-2-oxoethyl]amonium bromide (1f) f1 (ppm) CH 3 CN S22

23 Figure S25. 1 H NMR (DMSO-d 6 /dry HCl, 500 MHz): 2-(Methylamino)-1-(4-hydroxyphenyl)ethanone hydrochloride (1g) f1 (ppm) S23

24 Figure S C { 1 H} NMR (DMSO-d 6 /dry HCl, 126 MHz): 2-(Methylamino)-1-(4-hydroxyphenyl)ethanone hydrochloride (1g) S24

25 Figure S27. 1 H NMR (DMSO-d 6 /dry HCl, 50 0 MHz): 2-(Butylamino)-1-(4-hydroxyphenyl)ethanone hydrochloride (1h) f1 (ppm) S25

26 Figure S C { 1 H} NMR (DMSO-d 6 /dry HCl, 126 MHz): 2-(Butylamino)-1-(4-hydroxyphenyl)ethanone hydrochloride (1h) S26

27 Figure S29. UV-vis absorption in a) acetate buffer (ph = 4.02, c = mol dm 3 ), c (1f) = mol dm 3 ) (black solid line) and in b) phosphate buffer (ph = 8.37, c = mol dm 3 ), c (1f) = mol dm 3 ) (red solid line): triethyl[2-(4-hydroxyphenyl)-2- oxoethyl]amonium bromide (1f) / 10 4 mol 1 dm 3 cm 1 ~ / 10 4 cm / nm S27

28 Figure S30. Output spectrum of 40 W medium-pressure Hg discharge lamp equipped with a 313-nm-band-pass filter: λ em = ± 1.5 nm (bandwidth at half-height) I / a.u. ~ / 10 4 cm / nm S28