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ESInBu4NOTf-Promoted Radical Self-Hydrogen Transferring

Isomerization under Transition Metal-Free Conditions Hong-Xing Zheng,a,b Chuan-Zhi Yao,b Jian-Ping Qu,*a and Yan-Biao Kang*b

aInstitute of Advanced Synthesis, School of Chemistry and Molecular Engineering, Jiangsu National Synergetic Innovation Center for Advanced Materials, Nanjing Tech University, Nanjing 211816, China. E-mail: ias_jpqu@njtech.edu.cn b Centre of Advanced Nanocatalysis, Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, China. E-mail: ybkang@ustc.edu.cn

Contents1. General information S1

2. General procedures S1–S2

3. Kinetic study experiments S2–S11

4. References S11

5. NMR spectra S12–S17

1. General information

Toluene was dried over activated 4 Å molecular sieves and heated to reflux over sodium. 1H, 13C NMR

spectra were recorded on a Bruker 400 spectrometer; Chemical shifts are reported in δ units relative to

CDCl3 [1H δ = 7.26, 13C δ = 77.36].

2. General procedure

1 (0.5 mmol), tBuOK (10 mol%) and nBu4NOTf (10 mol%) were weighed directly into a Schlenk tube

and dried under high vacuum for 10 min. Toluene (1 mL) was added and stirred at 70 °C, the resulting

reaction mixture was monitored by TLC. The reaction crude product is purified by silica gel column.

1, 3-diphenylpropan-1-one (2a)Ph

O

Ph

98%.1H NMR (400 MHz, CDCl3)1 δ 7.98-7.95 (m, 2H), 7.58 – 7.54 (m, 1H), 7.48 – 7.45 (m, 2H), 7.33 –

7.19(m, 5H), 3.33 – 3.29 (m, 2H), 3.10 – 3.06 (m, 2H).

3-phenyl-1-(p-tolyl)propan-1-one (2b)

O

90%. 1H NMR (400 MHz, CDCl3)1 δ 7.86 (dd, J = 8.2, 1.8 Hz 2H), 7.32 – 7.18 (m, 7H), 3.29-3.25 (m,

2H), 3.06 (t, J = 7.4Hz), 2.40 (s, 3H).

Electronic Supplementary Material (ESI) for Organic Chemistry Frontiers.This journal is © the Partner Organisations 2018

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1-(4-chlorophenyl)-3-phenylpropan-1-one (2c)

O

Cl

82%. 1H NMR (400 MHz, CDCl3)1 δ 7.89 (dt, J = 9.1, 2.2 Hz, 2H), 7.43 (dt, J = 9.1, 2.2 Hz, 2H), 7.33 –

7.28 (m, 2H), 7.26 - 7.19 (m, 3H) 3.29 – 3.25 (m, 2H), 3.06 (t, J = 7.8Hz, 2H).

3-(4-fluorophenyl)-1-(p-tolyl)propan-1-one (2d)

O

F

84%. 1H NMR (400 MHz, CDCl3) δ7.85 (dt, J =8.4, 1.8 Hz 2H), 7.26 – 7.18 (m, 4H), 7.00 – 6.94 (m,

2H), 3.27 – 3.23 (m, 2H), 3.04 (t, J = 7.6 Hz, 2H), 2.41 (s, 3H).

1-(p-tolyl)-3-(4-(trifluoromethyl)phenyl)propan-1-one (2e)

O

CF3

95%.1H NMR (400 MHz, CDCl3) δ 7.86 (dt, J =8.6, 1.8 Hz, 2H), 7.55 (d, J =8.0 Hz, 2H), 7.37 (d, J =8.0

Hz, 2H), 7.27-7.25 (m, 2H), 3.32 – 3.28 (m, 2H), 3.13 (t, J = 7.4 Hz, 2H).

1-(naphthalen-1-yl)propan-1-one (2f)

O

59%.1H NMR (400 MHz, CDCl3)1 δ 8.57 (d, J = 7.6 Hz, 1H), 7.97 (d, J = 7.6 Hz, 1H), 7.88 – 7,83 (m,

2H), 7.61 – 7.47 (m, 4H), 3.08 (q, J = 7.2Hz, 2H ), 1.29 (t, J = 7.4 Hz, 3H).

Reference: (1) H.-X. Zheng, Z.-F. Xiao, C.-Z. Yao, C.-Z. Q.-Q. Li, X.-S. Ning and Y.-B. Kang, Y. Tang,

Org. Lett., 2015, 17, 6102.

3. Kinetic study

Ph Ph

OHtBuOK (4-10 mol%),nBu4OTf (4-10 mol %)

toluene, 50 C Ph Ph

O

1a 2a

All data was collected on 400 MHz 1H NMR using 1,3-dimethoxybenzene as the internal standard.

The initial rates were calculated as the slopes of time zero on the conversion curves of 1a against time.

3.1 The kinetic study on the dependence of the initial rate on [nBu4OTf].

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General procedure: 1a (0.75 mol, 157.5 mg) and nBu4OTf (4-10 mol%, 11.8-29.4 mg) were

weighed into a Schlenk tube. After dried in vacuo for 15 min, 2 mL of toluene was added. Under stirring,

tBuOK (10 mol %, 3.4 mg) and 1,3-dimethoxybenzene (33 μL, as internal standard) were added. The

resulting reaction mixture was stirred at 50 ̊C. At each sampling time 20 μL reaction mixture was

extracted and examined by 1H NMR parameters (400 MHz). 1a was determined using 1,3-

dimethoxybenzene as internal standard by 1H NMR parameters and the results were demonstrated in

Figure S1-4 and Table S2.

Figure 1. 1H NMR for [1a] = 0.375 M (0.75 mmol, 157.5 mg), tBuOK (10 mol %, 8.4 mg) and

nBu4OTf (4 mol %, 11.8 mg), toluene (2 μL), 50 C, 1,3-dimethoxybenzene (0.25 mmol, 33 μL) as

internal standard.

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Figure 2. 1H NMR for [1a] = 0.375 M (0.75 mmol, 157.5 mg), tBuOK (10 mol %, 8.4 mg) and

nBu4OTf (6 mol %, 17.6 mg), toluene (2 mL), 50 C, 1,3-dimethoxybenzene (0.25 mmol, 33 μL) as

internal standard.

Figure 3. 1H NMR for [1a] = 0.375 M (0.75 mmol, 157.5 mg), tBuOK (10 mol %, 8.4 mg) and

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nBu4OTf (8 mol %, 23.5 mg), toluene (2 mL), 50 C, 1,3-dimethoxybenzene (0.25 mmol, 33 μL) as

internal standard.

Figure 4. 1H NMR for [1a] = 0.375 M (0.75 mmol, 157.5 mg), tBuOK (10 mol %, 8.4 mg) and

nBu4OTf (10 mol %, 29.4 mg), toluene (2 mL), 50 C, 1,3-dimethoxybenzene (0.25 mmol, 33 μL) as

internal standard.

Table S3. Dependence of nBu4OTf: [1a] v.s. Time.

1a [mol/L]

4 mol% 6 mol% 8 mol% 10 mol%

Time(min

)M

Time(min

)M

Time(min

)M

Time(min

)M

0 0.375 0 0.375 0 0.375 0 0.375

15 0.35625 20 0.33553 20 0.30907 15 0.3

30 0.3375 40 0.28816 40 0.24313 30 0.25263

45 0.31875 60 0.23684 60 0.17308 45 0.17763

60 0.29625 80 0.18158 80 0.08654 60 0.09079

75 0.2775 75 0.03553

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3.2 The kinetic study on the dependence of the initial rate on [tBu4OK].

General procedure: (E)-1,3-diphenylprop-2-en-1-ol (0.75 mol, 157.5 mg) and nBu4OTf (10 mol%,

29.4 mg) were weighed into a Schlenk tube. After dried in vacuo for 15 min, 2mL of toluene was added.

Under stirring, tBuOK (4-10 mol%, 3.4-8.4mg) and 1,3-dimethoxybenzene (33 μL, as internal standard)

were added.The resulting reaction mixture was stirred at 50 ̊C. At each sampling time 20 μL reaction

mixture was extracted and examined by 1H NMR parameters (400 MHz). [(E)-1,3-diphenylprop-2-en-1-

ol] was determined using 1,3-dimethoxybenzene as internal standard by 1H NMR parameters and the

results were demonstrated in Figure S1-5 and Table S3.

Figure 5. 1H NMR for [1a] = 0.375 M (0.75 mmol, 157.5 mg), tBuOK (4 mol %, 3.4 mg) and

nBu4OTf (10 mol %, 29.4 mg), toluene (2 mL), 50 C, 1,3-dimethoxybenzene (0.25 mmol, 33 μL) as

internal standard.

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Figure 6. 1H NMR for [1a] = 0.375 M (0.75 mmol, 157.5 mg), tBuOK (6 mol %, 5.0 mg) and

nBu4OTf (10 mol %, 29.4 mg), toluene (2 mL), 50 C, 1,3-dimethoxybenzene (0.25 mmol, 33 μL) as

internal standard.

Figure 7. 1H NMR for [1a] = 0.375 M (0.75 mmol, 157.5 mg), tBuOK (8 mol %, 6.7 mg) and

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nBu4OTf (10 mol %, 29.4 mg), toluene (2 mL), 50 C, 1,3-dimethoxybenzene (0.25 mmol, 33 μL) as

internal standard.

Figure 8. 1H NMR for [(E)-1,3-diphenylprop-2-en-1-ol] = 0.375 M (0.75 mmol, 157.5 mg), tBuOK

(10 mol %, 8.4 mg) and nBu4OTf (10 mol %, 29.4 mg), toluene (2 mL), 50 C, 1,3-dimethoxybenzene

(0.25 mmol, 33 μL) as internal standard.

Table S3. Dependence of tBuOK: [(E)-1,3-diphenylprop-2-en-1-ol] v.s. Time.

1a [mol/L]

4 mol% 6 mol% 8 mol% 10 mol%

Time(min

)M

Time(min

)M

Time(min

)M

Time(min

)M

0 0.375 0 0.375 0 0.375 0 0.375

20 0.3355 20 0.3333 15 0.3276 15 0.3197

40 0.3039 40 0.2875 30 0.2881 30 0.2565

60 0.2842 60 0.2541 45 0.2486 45 0.2092

80 0.2447 80 0.2000 62 0.2013 60 0.1342

100 0.2171 100 0.1541 75 0.1539 75 0.0868

120 0.1855 120 0.1041

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3.3 The kinetic study on the dependence of the initial rate on [Allylic Alcohol 1a].

General procedure: 1a (0.75-0.9 mol, 157.5-189 mg) and nBu4OTf (10 mol%, 29.4 mg) were

weighed into a Schlenk tube. After dried in vacuo for 15 min, 2mL of toluene was added. Under stirring,

tBuOK (10 mol %, 8.4mg) and 1,3-dimethoxybenzene (33 μL, as internal standard) were added.The

resulting reaction mixture was stirred at 50 ̊C. At each sampling time 20 μL reaction mixture was

extracted and examined by 1H NMR parameters (400 MHz). [1a] was determined using 1,3-

dimethoxybenzene as internal standard by 1H NMR parameters and the results were demonstrated in

Figure S4、S9-11 and Table S4.

Figure 9. 1H NMR for [1a] = 0.400 M (0.80 mmol, 168 mg), tBuOK (10 mol %, 8.4 mg) and

nBu4OTf (10 mol %, 29.4 mg), toluene (2 mL), 50 C, 1,3-dimethoxybenzene (0.25 mmol, 33 μL) as

internal standard.

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Figure 10. 1H NMR for [1a] = 0.425 M (0.85 mmol, 179 mg), tBuOK (10 mol %, 8.4 mg) and

nBu4OTf (10 mol %, 29.4 mg), toluene (2 mL), 50 C, 1,3-dimethoxybenzene (0.25 mmol, 33 μL) as

internal standard.

Figure 11. 1H NMR for [(E)-1,3-diphenylprop-2-en-1-ol] = 0.450 M (0.90 mmol, 189 mg), tBuOK

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(10 mol %, 8.4 mg) and nBu4OTf (10 mol %, 29.4 mg), toluene (2 mL), 50 C, 1,3-dimethoxybenzene

(0.25 mmol, 33 μL) as internal standard.

Table S4. Dependence of C0: [1a] v.s. Time.

Time(min) 1a [mol/L]

0 0.375 0.400 0.425 0.450

15 0.375 0.4 0.425 0.3991

30 0.3197 0.3604 0.3786 0.3326

45 0.2565 0.3089 0.3245 0.2817

62 0.2092 0.2574 0.2666 0.2213

75 0.1342 0.1940 0.2125 0.1541

90 0.0868 0.1307 0.1452 -

4. References

1. Liu. S; Liebeskind, L. S. J. Am. Chem. Soc. 2008, 130, 6918.

2. Fukuzawa, S.; Fujinami, T.; Yamauchi, S.; Sakai, S. J. Chem. Soc. Perkin. Trans. 1986, 1, 1929.

3. Arai,N.; Azuma, K.; Nii, N.; Ohkuma, T. Angew. Chem. Int. Ed.2008, 47, 7457.

4. Adam, J. S.; McLaughlin, M. G.; Reid, J. P. ; Cook, M. J. Org. Biomol. Chem. 2013, 11, 7662.

5. Lu, J.-M.; Shi. M. Org. Lett., 2008, 10, 1943.

6. Wadhwa, K.; Chintareddy, V. R.; Verkade, J.G.; J .Org. Chem. 2009, 74, 6681.

7. Kanbayashi, N. ; Onitsuka, K. Angew. Chem. Int. Ed. 2011, 50, 5197.

8. Manzini, S.; Poater, A.; Nelson, D. J.; Cavallo, L.; Nolan, S. P. Chem. Sci. 2014, 5, 180.

9. Ding, B.; Zhang, Z.; Liu, Y.; Sugiya, M.; Imamoto, T.; Zhang, W. Org. Lett., 2013, 15, 3690.

10. Ueno, S.; Shimizu, R.; Kuwano, R. Angew. Chem. Int. Ed. 2009, 48, 4543.

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5. Spectra

Ph

O

Ph2a

S-13

O

2b

S-14

O

Cl 2c

S-15

O

F2d

S-16

O

CF32e

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llll

O

2f