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[Supporting Information]
Copper-Catalyzed Aerobic Alcohol Oxidation under Air in Neat
Water by Using a Water-Soluble Ligand
Guofu Zhang,*† Xingwang Han,† Yuxin Luan,† Yong Wang,† Xin Wen,† Chengrong Ding,† Li
Xu,*‡ Jianrong Gao†
†College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310014, ‡Department of Chemistry, Zhejiang University, Hangzhou 310027, People’s Republic of China. Fax: (+86)-571-8832-0147; Tel: (+86)-571-8832-0147; E-mail: *[email protected]; [email protected]
Table of Contents ------------------------------------------------------------------------------------------------------------------
General Expermental ......................................................................page S2
Experimental Sections................................................................page S3-S8
a) General Procedures for Synthesis of Pytl-β-CD
b) General Experimental Procedure for the Copper-Catalyzed Aerobic Alcohol Oxidation in Neat Water under Air
c) General Experimental Procedure for the Reuse of Cu/pytl-β-CD in the p-Tolylmethanol Oxidation
NMR Characterization Data and Figures of Products……......page S9-S31
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General Experimental
All reagents were purchased from commercial suppliers and used without purification
unless otherwise stated. All alcohols were purchased from Aladdin reagent Co., LTD
(Shanghai). β-Cyclodextrin, 2-ethynylpyridine, copper salts were purchased from
Sigma-Adrich Company. Column chromatography was performed with silica gel
(300-400 mesh) produced by Qingdao Marine Chemical Factory, Qingdao (China).
GC-MS analysis of determination of conversion was performed on the instrument of
Agilent 7890 GC-QQQ. NMR spectra were recorded on Bruker AVANCE III
500MHz instrument with TMS as internal standard. The FT-IR spectra were recorded
from KBr pellets in the range of 4000-400 cm-1 on Nicolet 6700.
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Experimental Sections.
a) General Experimental Procedures for Synthesis of Pytl-β-CD
(1) Synthesis of 6-O-Monotosyl-β-CD (I). β-Cyclodextrin (35.0 mmol) and NaOH
(500.0 mmol) were dissolved in water (800.0 mL) in a 2.0 L three-neck round-bottom
flask equipped with a magnetic stirrer. The temperature was maintained around
0-5 °C. p-Toluenesulfonyl chloride (TsCl, 140.0 mmol) was added, and the suspen-
sion was stirred vigorously for 4 h. Then the unreacted TsCl was removed by filtra-
tion. After that, the pH of filtrate was adjusted to neutral by the addition of hydro-
chloric acid, the product began to precipitate. Subsequently, the mixture was filtered,
washed with water, dried in vacuum and recrystallized by water. The final pure
6-O-monotosyl-β-CD was dried overnight in vacuum at 60 °C. Yield: 10.9644 g
(White solid, 24.3%). 1H NMR (500 MHz, DMSO-d6): δ (ppm) 7.77-7.72 (m, 2H),
7.45-7.40 (m, 2H), 5.73 (s, 14H), 4.85-4.77 (m, 7H), 4.50-4.32 (m, 6H), 3.67-3.53 (m,
28H), 3.51-3.29 (m, overlaps with HDO), 2.43 (s, 3H).
Figure S1. 1HNMR spectrum of 6-O-Monotosyl-β-CD.
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(2) Synthesis of 6-Monodeoxy-6-Monoazido-β-CD (II). 6-O-monotosyl-β-CD (5.0
mmol) and sodium azide (10.0 mmol) were dissolved in anhydrous DMF (30.0 mL).
The mixture was stirred at 75 °C for 4 h, after which H2O (20.0 mL) and acetone
(400.0 mL) were added orderly. Then, the product began to precipitate. After that, the
product was filtrated and washed with acetone twice (2×400.0 mL). The
6-monodeoxy-6-monoazido- β-CD was obtained as white solid powder after dried in
vacuum at 60 °C overnight. Yield: 5.4288 g (white powder, 93.6%). According to
FT-IR spectra, the absorption band at 2105.5 cm-1 clearly indicates the successful at-
tachment of azido group onto the β-cyclodextrin. 1H NMR (500 MHz, DMSO-d6): δ
(ppm) 5.81-5.63 (m, 14H), 4.88-4.83 (m, 7H), 4.56-4.45 (m, 6H), 3.77-3.56 (m, 28H),
3.40-3.29 (m, overlaps with HDO).
Figure S2. 1H NMR spectrum of 6-monodeoxy-6-monoazido-β-CD.
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443.
653
0.3
580.
8664
.270
6.77
56.486
2.8
945.
810
30.91
079.
31155
.6
1414
.3
1659
.8
2105
.5
2928
.1
-10
0
10
20
30
40
50
60
70
80
90%
T
1000 2000 3000 4000 Wavenumbers (cm-1)
Figure S3. FT-IR spectrum of 6-monodeoxy-6-monoazido-β-CD
(3) Synthesis of Pytl-β-CD. Under nitrogen atmosphere,
6-monodeoxy-6-monoazido-β-CD (3.0 mmol), 2-ethynylpyridine (3.6 mmol), sodium
ascorbate (0.6 mmol) and CuSO4 (0.3 mmol) were added into a 100 mL Schlenk tube
and dissolved in deaerated DMSO/H2O (v/v, 1/1, 40.0 mL). The resulting mixture
was stirred at room temperature for 24 h. After the reaction, water (20.0 mL) was
added. The obtained solution was poured into acetone (400.0 mL) and the desired tri-
azole functionalized β-CD (pytl-β-CD) began to precipitate. After the mixture had
been filtrated, washed with acetone (until the copper content was beyond the detection
limit of ICP-MS), dried under vacuum, pytl-β-CD was obtained as white solid powder.
Yield: 3.4880 g (white powder, 92.1%). From the FT-IR, the absorption band at
2105.5 cm-1 disappeared and showed a new band at 1604.8 cm-1, which was assigned
to the C=C vibration of the triazole ring and implied the completion of click pro-
cess. 1H NMR (500 MHz, DMSO-d6): δ (ppm) 8.59 (d, 1H), 8.56 (s, 1H), 8.03 (d,
1H), 7.90 (t, 1H), 7.35 (t, 1H), 5.90-5.61 (m, 14H), 4.93-4.71 (m, 7H), 4.54-4.41 (m,
6H), 3.94-3.57 (m, 28H), 3.46-3.26 (m, overlaps with HDO); ESI-MS: 1263.4 (The
major ion was assigned to the [pytl-β-CD +H]+ species).
“ N3 “
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530.
358
3.070
8.4755.
1872.
394
6.4
1033
.310
80.3
1155
.9
1365
.414
22.6
1636
.6
2926
.6
30
40
50
60
70
80
90
100
%T
1000 2000 3000 4000 Wavenumbers (cm-1)
Figure S4. FT-IR spectrum of ptyl-β-CD.
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44x10x10
00
0.0.2
0.0.4
0.0.6
0.0.8
11
1.1.2
1.1.4
1.1.6
1.1.8
22
2.2.2
1263.41263.4
250.0250.0
330.3330.3
696.2696.2
Figure S5. ESI-MS spectrum of ptyl-β-CD.
Figure S6. Partial 1H NMR spectrum of ptyl-β-CD.
b) General Experimental Procedure for the Copper-Catalyzed Aero-bic Alcohol Oxidation in Neat Water under Air.
A mixture of alcohol (1.0 mmol), Cu(OAc)2·H2O (0.05 mmol), pytl-β-CD (0.05
mmol), TEMPO (0.05 mmol), Na2CO3 (1.0 mmol), H2O (4.0 mL) was added to a 100
mL tube, which was vigorously stirred in air under reflux for 10-24 h. After the reac-
tion, the product was extracted with CH2Cl2 (3×2.0 mL). The combined organic
phase was washed by water (3.0 mL) and dried by anhydrous MgSO4. After concen-
tration in vacuum, the residue was purified by column chromatography to afford the
desired aldehyde. The pure product was subjected to 1H NMR and 13C NMR analy-
sis.
c) General Experimental Procedure for the Reuse of Cu/pytl-β-CD in the p-Tolylmethanol Oxidation
A mixture of p-tolylmethanol (1.0 mmol), Cu(OAc)2·H2O (0.05 mmol), pytl-β-CD
(0.05 mmol), TEMPO (0.05 mmol), Na2CO3 (1.0 mmol), H2O (4.0 mL) was added to
a 100 mL tube, which was vigorously stirred in air under reflux. After the reaction, the
[ptyl-β-CD+H]+
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product was extracted with CH2Cl2 (3×2.0 mL). The combined organic phase was
washed by water (3.0 mL) and dried by anhydrous MgSO4. After concentration in
vacuum, the residue was purified by column chromatography to afford aldehyde. The
pure product was subjected to 1H NMR and 13C NMR analysis. The next run was
performed by adding fresh alcohol (1.0 mmol) and TEMPO (0.05 mmol) to the aque-
ous media.
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NMR Characterization Data and Figures of Products
O
Benzaldehyde (Table 2, entry 1) 1H NMR (500 MHz, CDCl3): δ
7.53(t, J = 7.8 Hz, 2H), 7.61-7.65(m, 1H), 7.87-7.90(m, 2H), 10.02(s, 1H). 13C NMR
(125 MHz, CDCl3): δ 128.9, 129.7, 134.4, 136.4, 192.3.
H3C
O
4-Methylbenzaldehyde (Table 2, entry 2) 1H NMR (500 MHz,
CDCl3): δ 2.44(s, 3H), 7.34(d, J = 8.0 Hz, 2H), 7.78(d, J = 8.0 Hz, 2H), 9.97(s,
1H). 13C NMR (125 MHz, CDCl3): δ 21.8, 129.7, 129.8, 134.2, 145.5, 191.9.
MeO
O
4-Methoxybenzaldehyde (Table 2, entry 3) 1H NMR (500 MHz, CDCl3): δ 3.90(s, 3H), 7.00-7.03(m, 2H), 7.83-7.87(m, 2H), 9.89(s, 1H). 13C
NMR (125 MHz, CDCl3): δ 55.5, 114.3, 129.9, 131.9, 164.6, 190.8.
O
1-Naphthaldehyde (Table 2, entry 4) 1H NMR (500 MHz, CDCl3): δ
7.57(t, J = 7.5 Hz, 2H), 7.66-7.70(m, 1H), 7.89(d, J = 8.0 Hz, 1H), 7.93(dd, J1= 8.0,
1.5 Hz, 1H), 9.26(d, J = 9.0 Hz, 1H), 10.37(s, 1H). 13C NMR (125 MHz, CDCl3): δ
124.7, 126.8, 128.3, 128.9, 130.3, 131.2, 133.5, 135.1, 136.4, 193.3.
H3CCH3
O
3,4-Dimethylbenzaldehyde (Table 2, entry 5) 1H NMR (500
MHz, CDCl3): δ 2.30(d, J = 4.0 Hz, 6H), 7.25(d, J = 8.0 Hz, 1H), 7.58(t, J = 14.0 Hz,
2H), 9.89(s, 1H). 13C NMR (125 MHz, CDCl3): δ 19.4, 20.0, 127.5, 130.0, 130.4,
134.4, 137.3, 144.1, 192.0.
H3COOCH3
O
3,4-Dimethoxybenzaldehyde (Table 2, entry 6) 1H NMR (500
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MHz, CDCl3): δ 3.94(d, J = 13.5 Hz, 6H), 6.97(d, J = 8.0 Hz, 1H), 7.39(d, J = 2.0 Hz,
2H), 7.43-7.45(q, 1H), 9.84(s, 1H). 13C NMR (125 MHz, CDCl3): δ 55.9, 56.1, 108.9,
113.4, 126.8, 130.1, 149.6, 154.4, 190.8.
OMe
O
2-Methoxybenzaldehyde (Table 2, entry 7) 1H NMR (500 MHz, CDCl3): δ 3.95(s, 3H), 7.00-7.07(m, 2H), 7.55-7.60(m, 1H), 7.84-7.86(q, 1H), 10.49(s,
1H). 13C NMR (125 MHz, CDCl3): δ 55.5, 111.6, 120.6, 125.0, 128.5, 135.9, 161.8,
189.8.
Cl
O
2-Clorobenzaldehyde (Table 2, entry 8) 1H NMR (500 MHz, CDCl3): δ 7.34(t, J = 7.5 Hz, 1H), 7.39-7.42(q, 1H), 7.47-7.51(m, 1H), 7.86-7.88(q, 1H),
10.43(s, 1H). 13C NMR (125 MHz, CDCl3): δ 127.1, 129.2, 130.4, 132.3, 135.0,
137.7, 189.5.
Cl
O
3-Clorobenzaldehyde (Table 2, entry 9) 1H NMR (500 MHz, CDCl3): δ 7.47(t, J = 7.8 Hz, 1H), 7.57-7.60(m, 1H), 7.74-7.77(m, 1H), 7.84(t, J = 1.7 Hz, 1H),
9.96(s, 1H). 13C NMR (125 MHz, CDCl3): δ 127.9, 129.2, 130.3, 134.3, 135.4, 137.8,
190.7.
Cl
O
4-Clorobenzaldehyde (Table 2, entry 10) 1H NMR (500 MHz, CDCl3): δ 7.49-7.53(dt, J = 9.5, 7.5 Hz, 2H), 7.81-7.84(m, J = 13.0 Hz, 2H), 9.96(s,
1H). 13C NMR (125 MHz, CDCl3): δ 129.4, 130.8, 134.7, 140.9, 190.8.
Br
O
4-Bromobenzaldehyde (Table 2, entry 11) 1H NMR (500 MHz, CDCl3): δ 7.69-7.72(q, 2H), 7.75-7.78(m, 2H), 9.99(s, 1H). 13C NMR (125 MHz,
CDCl3): δ 129.9, 131.0, 132.4, 135.0, 191.0.
O2N
O
4-Nitrobenzaldehyde (Table 2, entry 12) 1H NMR (500 MHz,
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CDCl3): δ 8.09(dd, J = 7.0, 2.0 Hz, 2H), 8.41(d, J = 8.5 Hz, 2H), 10.17(s, 1H). 13C
NMR (125 MHz, CDCl3): δ 124.3, 130.4, 140.0, 151.1, 190.2.
F
O
4-Fluorobenzaldehyde (Table 2, entry 13) 1H NMR (500 MHz, CDCl3): δ 7.16-7.20(m, 2H), 7.87-7.90(m, 2H), 9.94(s, 1H). 13C NMR (125 MHz,
CDCl3): δ 116.3, 132.4, 133.0, 164.8, 191.6.
Cl Cl
O
2,4-Diclorobenzaldehyde (Table 2, entry 14) 1H NMR (500 MHz, CDCl3): δ 7.37(q, J = 10.0 Hz, 1H), 7.47(d, J = 2.0 Hz, 1H), 7.86(d, J = 8.5 Hz,
1H), 10.40(s, 1H). 13C NMR (125 MHz, CDCl3): δ 127.9, 130.3, 130.4, 130.9, 138.5,
141.0, 188.4.
N
O
3-Nicotinaldehyde (Table 2, entry 15) 1H NMR (500 MHz, CDCl3): δ 7.46-7.50(q, 1H), 8.15-8.18(m, 1H), 8.82-8.84(q, 1H), 9.07(d, J = 2.0 Hz, 1H),
10.10(s, 1H). 13C NMR (125 MHz, CDCl3): δ 124.0, 131.4, 135.7, 151.9, 154.6,
190.6.
SO 2-Thiopheneformaldehyde (Table 2, entry 16) 1H NMR (500 MHz,
CDCl3): δ 7.18-7.21(q, 1H), 7.74-7.75(q, 1H), 7.77(dd, J = 3.5, 1.5 Hz, 1H), 9.91(d, J
= 1.5 Hz, 1H). 13C NMR (125 MHz, CDCl3): δ 128.2, 135.0, 136.3, 143.8, 182.9.
OO 2-Furaldehyde (Table 2, entry 17) 1H NMR (500 MHz, CDCl3): δ
6.53-6.55(q, 1H), 7.20(t, J = 1.8 Hz, 1H), 7.63(d, J = 1.0 Hz, 1H), 9.58(s, 1H). 13C
NMR (125 MHz, CDCl3): δ 112.5, 121.2, 148.1, 152.9, 177.8.
O
Cinnamaldehyde (Table 2, entry 18) 1H NMR (500 MHz,
CDCl3): δ 6.71(q, J = 7.5 Hz, 1H), 7.42(d, J = 2.0 Hz, 1H), 7.43(d, J = 2.0 Hz, 2H),
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7.45(d, J = 2.5 Hz, 1H), 7.55(d, J = 2.5 Hz, 1H), 7.56(d, J = 2.0 Hz, 1H), 9.69(d, J =
7.0 Hz, 1H). 13C NMR (125 MHz, CDCl3): δ 128.5, 129.1, 131.2, 134.0, 152.7, 193.8. O
Acetophenone (Table 2, entry 19) 1H NMR (500 MHz, CDCl3): δ 2.62(s, 3H), 7.47(t, J = 7.5 Hz, 2H), 7.57(t, J = 7.5 Hz, 1H), 7.97(d, J = 7.5 Hz,
2H). 13C NMR (125 MHz, CDCl3): δ 26.5, 128.2, 128.4, 133.0, 137.0, 198.0.
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Figure 1. 1H NMR and 13C NMR spectra of benzaldehyde.
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Figure 2. 1H NMR and 13C NMR spectra of p-tolualdehyde.
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Figure 3. 1H NMR and 13C NMR spectra of 4-methoxybenzaldehyde.
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Figure 4. 1H NMR and 13C NMR spectra of 1-naphthaldehyde
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Figure 5. 1H NMR and 13C NMR spectra of 3,4-dimethylbenzaldehyde
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Figure 6. 1H NMR and 13C NMR spectra of 3,4-dimethoxybenzaldehyde
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Figure 7. 1H NMR and 13C NMR spectra of 2-methoxybenzaldehyde.
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Figure 8. 1H NMR and 13C NMR spectra of 2-chlorobenzaldehyde
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Figure 9. 1H NMR and 13C NMR spectra of 3-chlorobenzaldehyde
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Figure 10. 1H NMR and 13C NMR spectra of 4-chlorobenzaldehyde.
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Figure 11. 1H NMR and 13C NMR spectra of 4-bromobenzaldehyde.
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Figure 12. 1H NMR and 13C NMR spectra of 4-nitrobenzaldehyde.
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Figure 13. 1H NMR and 13C NMR spectra of 4-fluorobenzaldehyde.
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Figure 14. 1H NMR and 13C NMR spectra of 2,4-dichlorobenzaldehyde.
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Figure 15. 1H NMR and 13C NMR spectra of 3-nicotinaldehyde.
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Figure 16. 1H NMR and 13C NMR spectra of 2-thiophenecarboxaldehyde.
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Figure 17. 1H NMR and 13C NMR spectra of furfural.
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Figure 18. 1H NMR and 13C NMR spectra of cinnamaldehyde.
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Figure 19. 1H NMR and 13C NMR spectra of acetophenone.
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