A family of stilbene-ethers as photolabile protecting groups for primary alcohols

offers controlled deprotection based on choice of wavelength

Jinn-Hsuan Ho*, Ya-Wen Lee, Ying-Zhe Chen, Pin-Sian Chen, Wei-Qi Liu, and Yi-Shun Ding

Department of Chemical Engineering, National Taiwan University of Science and Technology.

E-mail: jhho@mail.ntust.edu.tw

Contents

1. 1H and

13C NMR of trans-1-(3-phenylpropoxy)-4-styrylbenzene (trans-1a)

2. 1H and

13C NMR of cis-1-(3-phenylpropoxy)-4-styrylbenzene (cis-1a)

3. 1H and

13C NMR of trans-2-{2-[4-(3-phenylpropoxy)-phenyl]-vinyl}-furan (trans-1b)

4. 1H and

13C NMR of cis-2-{2-[4-(3-phenylpropoxy)-phenyl]-vinyl}-furan (cis-1b)

5. 1H and

13C NMR of trans-2-{2-[4-(3-phenylpropoxy)-phenyl]-vinyl}-thiophene (trans-1c)

6. 1H and

13C NMR of cis-2-{2-[4-(3-phenylpropoxy)-phenyl]-vinyl}-thiophene (cis-1c)

7. 1H and

13C NMR of trans-4-{2-[4-(3-phenylpropoxy)-phenyl]-vinyl}-benzonitrile (trans-1d)

8. 1H and

13C NMR of cis-4-{2-[4-(3-phenylpropoxy)-phenyl]-vinyl}-benzonitrile (cis-1d)

9. 1H and

13C NMR of trans-1-ethoxy-4-(4-styrylphenoxy)benzene (trans-1e)

10. 1H and 13

C NMR of trans-1-propyl-4-(4-styrylphenoxy)benzene (trans-1f)

11. 1H and 13

C NMR of trans-2-(4-styrylphenoxy)naphthalene (trans-1g)

12. 1H and 13

C NMR of 1-benzyloxy-4-(trans-styryl)benzene (trans-1h)

13. 1H and 13

C NMR of 1-(cinnamyloxy)-4-(trans-styryl)benzene (trans-1i)

14. 1H NMR of trans-4-(naphthalen-2-yl)-but-3-en-2-one (trans-2a)

15. 1H NMR of trans-4-(benzo[b]furan-5-yl)-but-3-en-2-one (trans-2b)

16. 1H NMR of trans-4-(benzo[b]thiophen-5-yl)-but-3-en-2-one (trans-2c)

17. 1H NMR of trans-7-(3-oxo-but-1-enyl)-naphthalene-2-carbonitrile (trans-2d)

18. 1H and 13

C NMR of trans-4-fluorostilbene (trans-3a)

19. 1H and 13

C NMR of trans-4-fluorostyrylfuran (trans-3b)

20. 1H and 13

C NMR of trans-4-fluorostyrylthiophene (trans-3c)

21. 1H and 13

C NMR of 4-phenylbutan-2-ol (11)

22. 1H and 13

C NMR of 2-methyl-4-phenylbutan-2-ol (12)

23. 1H and 13

C NMR of 4-(3-phenylpropoxy)-benzaldehyde (A) (reactant for cis and trans-1d)

24. Test Experiment for Examining the Formation of Acid in Dichloromethane.

1H NMR of trans-1a

13

C NMR of trans-1a

O

(1a) trans

O

(1a) trans

1H NMR of cis-1a

13

C NMR of cis-1a

O

(1a) cis

O

(1a) cis

1H NMR of trans-1b

13

C NMR of trans-1b

OO

(1b) trans

OO

(1b) trans

1H NMR of cis-1b

13C NMR of cis-1b

O

(1b) cis

O

O

(1b) cis

O

1H NMR of trans-1c

13C NMR of trans-1c

SO

(1c) trans

SO

(1c) trans

1H NMR of cis-1c

13C NMR of cis-1c

O

(1c) cis

S

O

(1c) cis

S

1H NMR of trans-1d

13C NMR of trans-1d

O

(1d) trans

NC

O

(1d) trans

NC

1H NMR of cis-1d

13C NMR of cis-1d

O

(1d) cisCN

O

(1d) cisCN

1H NMR of trans-1e

13

C NMR of trans-1e

O

O

1e

O

O

1e

1H NMR of trans-1f

13

C NMR of trans-1f

O1f

O1f

1H NMR of trans-1g

13

C NMR of trans-1g

O

1g

O

1g

1H NMR of trans-1h

13C

NMR of trans-1h

O

trans-1h

O

trans-1h

1H NMR of trans-1i

13

C NMR of trans-1i

O

1i

O

1i

1H NMR of trans-2a

1H NMR of trans-2b

O

(2a) trans

(2b) trans

O

O

1H NMR of trans-2c

1H NMR of trans-2d

(2c) trans

S

O

O

(2d) trans

NC

1H NMR of trans-3a

13

C NMR of trans-3a

Ftrans-3a

Ftrans-3a

1H NMR of trans-3b

13

C NMR of trans-3b

F

O

trans-3b

F

O

trans-3b

1H NMR of trans-3c

13

C NMR of trans-3c

F

S

trans-3c

F

S

trans-3c

1H NMR of 5

13

C NMR of 5

OH

11

OH

11

1H NMR of 6

13

C NMR of 6

OH

12

OH

12

1H NMR of A

13

C NMR of A

O

H

O

A

O

H

O

A

24. Test Experiment for Examining the Formation of Acid in Dichloromethane:

We prepared 3 samples in quartz tubes as the following condition.

Tube1: Dichloromethane (20 mL) without irradiation.

Tube2: Dichloromethane (20 mL) under 300 nm-irradiation for 3 hours.

Tube3: Dichloromethane (20 mL) and compound 1a (20 mg) under 300 nm-irradiation for 3 hours.

After irradiation, we put few amount of 2-(4-(N,N-dimethylamino)styryl)quinoline (StQ) into the

quartz tubes. If the sample contains acid, protonated StQ will be obtained and the solution will

become red in color. If the sample does not contain acid, StQ will make the solution in light yellow

color.S1

The results of the test are shown in Fig S1. Unirradiated dichloromethane did not contain acid

(Tube1), but after irradiation, dichloromethane became acidic (Tube2). If irradiating

dichloromethane solution of 1a, the solution became even more acidic (Tube 3).

Fig. S1 The acidity of dichloromethane (DCM) tested by 2-(4-(N,N-dimethylamino)styryl)quinoline

(StQ). Tube1: unirradiated DCM; Tube2: irradiated DCM; Tube3: irradiated DCM solution of 1a.

Ref S1: Wang, S.-L.; Ho, T.-I. Chem. Phys. Lett. 1997, 268, 434.

N

N

N

N

HCl

HCl

light yellow in CH2Cl2 red in CH2Cl2

StQ Protonated StQ