Supporting Information
An Efficient and General Method for Formylation of Aryl Bromides
with CO2 and Poly(methylhydrosiloxane)
Bo Yu, Zhenzhen Yang, Yanfei Zhao, Leiduan Hao, Hongye Zhang, Xiang Gao, Buxing Han,
and Zhimin Liu*[a]
chem_201504320_sm_miscellaneous_information.pdf
Supporting Information
This file includes:
1. 1H NMR spectra of the reaction of CO2 and PMHS in the presence of Pd(DPPP)Cl2.(Figure S1)
2. 1H NMR and 13C NMR data of the products.
3. References (S1-S3)
4. 1H NMR and 13C NMR spectra of the products (Figure S2-20).
1.
Fig. S1 1H NMR spectra of the reaction of CO2 and PMHS in the presence of Pd(DPPP)Cl2. (A) pure PMHS
in CDCl3; (B) reaction mixture after the reaction of CO2 with PMHS catalyzed by Pd(DPPP)Cl2. Reaction condition:
CO2 (1 MPa), PMHS (Si-H: 15mmol) and Pd(DPPP)Cl2 (30 mg) in DMF, 100oC, 15h. 0.5 mL of CDCl3 solution
of the reaction mixture was transferred into the NMR tube. The spectrum showed the signal of pure PMHS (▲) and
the formation of silyl formate (◆). Two large signals at 2.7 ppm and 7.9 ppm are for DMF solvent (✿).
2. 1H and 13C NMR data of the isolated products
Benzaldehyde (Table 1, 3A) The compound was prepared according to the general procedure and
was subjected to column chromatography on silica gel, affording an isolated yield of 81% (171 mg, 1.62 mmol).
The characterization data obtained for benzaldehyde were identical to those previously reported in the literature
(S1). 1H NMR (CDCl3, 400 MHz): δ 7.43-7.47 (m, 2 H), 7.53-7.57 (m, 1 H), 7.79-7.81 (m, 2 H), 9.94 (s, 1 H);
13C NMR (CDCl , 100 MHz): δ 128.7, 129.4, 134.2, 136.2, 192.0.
3
4-Methylbenzaldehyde (Table 1, 3B) The compound was prepared according to the general
procedure and was subjected to column chromatography on silica gel with methanol/dichloromethane as the
eluent, affording an isolated yield of 85% (204 mg, 1.7 mmol). The characterization data obtained for
benzaldehyde were identical to those previously reported in the literature (S1). 1H NMR (CDCl3, 400 MHz):
δ2.30 (s, 3H), 7.20 (d, J = 8.0, 2H), 7.64 (d, J = 8.1, 2H), 9.83 (s, 1H); 13C NMR (CDCl3, 100 MHz): δ 21.6,
129.6, 129.7, 134.3, 145.3, 191.6.
2-Methylbenzaldehyde (Table 1, 3C) The compound was prepared according to the general
procedure and was subjected to column chromatography on silica gel, affording an isolated yield of 70% (168
mg, 1.4 mmol). The characterization data obtained for benzaldehyde were identical to those previously reported
in the literature (S1). 1H NMR (CDCl3, 400 MHz): δ = 2.67 (s, 3H), 7.25 (d, J=7.2 Hz, 1H), 7.34 (m, 1H), 7.45
(m, 1H), 7.79 (d, J=7.6 Hz, 1H), 10.26 (s, 1H); 13C NMR (CDCl3,100 MHz) δ = 19.2, 126.3, 131.8, 132.2, 133.6,
140.6, 192.6.
3-Methylbenzaldehyde (Table 1, 3D) The compound was prepared according to the general
procedure and was subjected to column chromatography on silica gel with ethyl acetate/dichloromethane as the
eluent, affording an isolated yield of 76% (182 mg, 1.52 mmol). The characterization data obtained for
benzaldehyde were identical to those previously reported in the literature (S2). 1H NMR (CDCl3, 400 MHz): δ
2.37 (s, 3 H), 7.38-7.41 (m , 2 H), 7.63-7.67 (m, 2 H), 9.93 (s, 1H); 13C NMR (CDCl3, 100 MHz): δ 20.7, 126.8,
128.5, 129.6, 134.9, 136.2, 138.5, 192.0;
3-Methoxylbenzaldehyde (Table 1, 3E) The compound was prepared according to the general
procedure and was subjected to column chromatography on silica gel with ethyl acetate/dichloromethane as the
eluent, affording an isolated yield of 75% (204 mg, 1.5 mmol). The characterization data obtained for
benzaldehyde were identical to those previously reported in the literature (S1). 1H NMR (CDCl3, 400 MHz) δ
7.20-7.15 (m, 1H), 7.39 (d, J = 1.7 Hz, 1 H), 7.44 (d, J = 6.7 Hz, 2 H), 9.97 (s, 1 H); 13C NMR (100 MHz,
CDCl3) δ 192.06, 160.19, 137.85, 130.02, 123.52, 121.51, 112.08, 55.45.
4-Methoxylbenzaldehyde (Table 1, 3F) The compound was prepared according to the
general procedure and was subjected to column chromatography on silica gel with ethyl
acetate/dichloromethane as the eluent, affording an isolated yield of 89% (242 mg, 1.78 mmol). The
characterization data obtained for benzaldehyde were identical to those previously reported in the literature (S1).
1H NMR (CDCl , 400 MHz) δ 3.72 (s, 3H), 6.83 (d, J = 8.8 Hz, 2 H), 7.67 (d, J = 8.8 Hz, 2 H), 9.74 (s, 1 H);
3
13C NMR (CDCl , 100 MHz) δ 55.2, 114.2, 128.2, 131.8, 164.6, 190.1;
3
2-Methoxylbenzaldehyde (Table 1, 3G) The compound was prepared as described procedure
and subjected to column chromatography on silica gel, affording an isolated yield of 59% (160 mg, 1.18 mmol).
The characterization data obtained for benzaldehyde were identical to those previously reported in the literature
(S1).1H NMR (CDCl3, 400 MHz) δ 3.92 (s, 3H), 7.01 (dd, J = 16.5, 8.1 Hz, 2H), 7.54 (dd, J = 11.4, 4.2 Hz,
1H), 7.82 (d, J = 7.6 Hz, 1H), 10.47 (s, 1H); 13C NMR (CDCl3, 100 MHz) δ 55.5, 111.6, 120.6, 124.8, 128.4,
135.8, 161.8, 190.0;
4-Isopropylbenzaldehyde (Table 1, 3I) The compound was prepared as described procedure and
subjected to column chromatography on silica gel, affording an isolated yield of 81% (262 mg, 1.62 mmol).
The characterization data obtained for benzaldehyde were identical to those previously reported in the literature
(S3). 1H NMR (400 MHz, CDCl3) δ 9.97 (s, 1H), 7.44 (d, J = 6.7 Hz, 2H), 7.39 (d, J = 1.7 Hz, 1H), 7.20 – 7.15
(m, 1H), 3.86 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 193.50, 136.64, 135.29, 133.76, 131.45, 130.57, 129.08,
128.48, 126.98, 124.89.
4-Chlorobenzaldehyde (Table 1, 3J) The compound was prepared as described procedure
and subjected to column chromatography on silica gel, affording an isolated yield of 75% (218 mg, 1.5 mmol).
The characterization data obtained for benzaldehyde were identical to those previously reported in the literature
(S1). 1H NMR (CDCl3, 400 MHz) δ 7.45-7.48 (m, 2 H), 7.77-7.79 (m, 2 H), 9.95 (s, 1 H); 13C NMR (CDCl3,
100 MHz) δ 129.4, 130.8, 134.8, 140.9, 190.4;
4-Fluorobenzaldehyde (Table 1, 3K) The compound was prepared as described procedure
and subjected to column chromatography on silica gel, affording an isolated yield of 78% (193 mg, 1.56 mmol).
The characterization data obtained for benzaldehyde were identical to those previously reported in the literature
(S1). 1H NMR (CDCl3, 400 MHz) δ 7.09-7.14 (m, 2 H), 7.83-7.84 (m, 2 H), 9.89 (s, 1 H); 13C NMR (CDCl3,
100 MHz) δ 116.5, 132.3, 133.3, 168.0, 189.9;
4-(Trifluoromethyl)-benzaldehyde (Table 1, 3L) The compound was prepared as described
procedure and subjected to column chromatography on silica gel, affording an isolated yield of 61% (215 mg,
1.22 mmol). The characterization data obtained for benzaldehyde were identical to those previously reported in
the literature (S1). 1H NMR (CDCl3, 400 MHz) δ 7.85-7.69 (m, 2H), 7.97 (d, J= 7.7 Hz ,2H), 10.07 (s, 1H). 13C
NMR (CDCl3, 100 MHz) δ 124.9, 126.1, 126.2, 129.9, 135.5, 138.8, 191.2;
1,4-Phthalaldehyde (Table 1, 3M) The compound was prepared as described procedure
and subjected to column chromatography on silica gel, affording an isolated yield of 65% (174 mg, 1.30 mmol).
The characterization data obtained for benzaldehyde were identical to those previously reported in the literature
(S3). 1H NMR (CDCl3, 400 MHz) δ 8.05 (s, 4H), 10.13 (s, 2H). 13C NMR (CDCl3, 100 MHz) δ 130.1, 140.0,
191.5;
Terephthaldehyde (Table 1, 3P) The compound was prepared as described procedure
and subjected to column chromatography on silica gel, affording an isolated yield of 74% (274 mg, 1.48 mmol).
The characterization data obtained for benzaldehyde were identical to those previously reported in the literature
(S1). 1H NMR (CDCl3, 400 MHz): δ 7.42 (t, J = 7.3 Hz, 1H), 7.49 (t, J = 7.4 Hz, 2H), 7.64 (d, J = 7.3 Hz, 2H),
7.76 (d, J = 8.2 Hz, 2H), 7.96 (d, J = 8.2 Hz, 2H), 10.06 (s, 1H). 13C NMR (CDCl3, 100 MHz) δ 127.4, 127.7,
128.5, 129.0, 130.3, 135.2, 139.7, 147.2, 191.9;
1-Naphthaldehyde (Table 1, 3Q) The compound was prepared as described procedure and
subjected to column chromatography on silica gel, affording an isolated yield of 76% (237 mg, 1.52 mmol).
The characterization data obtained for benzaldehyde were identical to those previously reported in the literature
(S1). 1H NMR (CDCl3 , 400 MHz) δ7.47 (dd, J = 10.4, 4.8 Hz, 2H), 7.56 (d, J = 7.6 Hz, 1H), 7.80 (dd, J = 16.8,
7.6 Hz, 2H), 7.94 (d, J = 8.2 Hz, 1H), 9.17 (d, J = 8.6 Hz, 1H), 10.27 (s, 1H). 13C NMR (CDCl3, 100 MHz) δ
124.7, 124.8, 126.8, 128.3, 128.8, 130.4, 131.3, 133.6, 135.0, 136.4, 193.1;
2-Naphthaldehyde (Table 1, 3R) The compound was prepared as described procedure and
subjected to column chromatography on silica gel, affording an isolated yield of 71% (222 mg, 1.42 mmol).
The characterization data obtained for benzaldehyde were identical to those previously reported in the literature
(S1). 1H NMR (CDCl3 , 400 MHz) δ 10.17 (s, 1H), 8.34 (s, 1H), 8.13 – 7.80 (m, 4H), 7.74 – 7.53 (m, 2H). 13C
NMR (101 MHz, CDCl3) δ 192.22, 136.48, 134.50, 134.16, 132.68, 129.54, 129.11, 128.09, 127.10, 122.81.
3-Thiophenecarboxaldehyde (Table 1, 3S) The compound was prepared as described procedure
and subjected to column chromatography on silica gel, affording an isolated yield of 80% (179 mg, 1.6 mmol).
The characterization data obtained for benzaldehyde were identical to those previously reported in the literature
(S1). 1H NMR (CDCl3, 400 MHz) δ 7.36 (s, 1 H), 7.54 (d, J = 4.7 Hz, 1 H), 8.11 (s, 1 H), 9.93 (s, 1H); 13C
NMR (CDCl3, 100 MHz) δ 124.4, 126.3, 135.5, 142.2, 183.8;
2-Thiophenecarboxaldehyde (Table 1, 3T) The compound was prepared as described procedure
and subjected to column chromatography on silica gel, affording an isolated yield of 73% (164 mg, 1.46 mmol).
The characterization data obtained for benzaldehyde were identical to those previously reported in the literature
(S1). 1H NMR (CDCl3, 400 MHz) δ 7.19 (dd, J = 4.0, 4.8 Hz, 1 H), 7.77-7.79 (m, 2 H), 9.93 (s, 1H); 13C NMR
(CDCl3, 100 MHz) δ 128.1, 134.7, 136.2, 143.6, 183.6;
4-Nitrobenzaldehyde (Table 2, 4K) The compound was prepared as described procedure
and subjected to column chromatography on silica gel, affording an isolated yield of 54% (163 mg, 1.1 mmol).
The characterization data obtained for benzaldehyde were identical to those previously reported in the literature
(S3). 1H NMR (CDCl3, 400 MHz) δ 7.73-7.77 (m, 1 H), 8.20-8.23 (m, 1 H), 8.46-8.49 (m, 1 H), 8.69 (s, 1H),
10.10 (s, 1 H); 13C NMR (CDCl3, 100 MHz) δ 124.4, 128.5, 130.4, 134.6, 137.3, 148.7, 189.7;
3-Pyridinecarboxaldehyde (Table 1, 4O) The compound was prepared as described procedure
and subjected to column chromatography on silica gel, affording an isolated yield of 89% (190 mg, 1.78 mmol).
The characterization data obtained for benzaldehyde were identical to those previously reported in the literature
(S1). 1H NMR (CDCl3, 400 MHz) δ 7.19 (dd, J = 4.0, 4.8 Hz, 1 H), 7.77-7.79 (m, 2 H), 9.93 (s, 1H); 13C NMR
(CDCl3, 100 MHz) δ 123.4, 130.7, 135.1, 151.2, 153.9, 190.3
3. References:
S1. Natte, K. Dumrath, A. Neumann, H. & Beller, M. Palladium-Catalyzed Carbonylations of
Aryl Bromides using Paraformaldehyde: Synthesis of Aldehydes and Esters. Angew. Chem. Int.
Ed. 53, 10090-10094 (2014).
S2.
Gonzalez-de-Castro, A. & Xiao, J. L. Green and Efficient: Iron-Catalyzed Selective
Oxidation of Olefins to Carbonyls with O2. J. Am. Chem. Soc. 137, 8206-8218 (2015).
S3. Jiang, X. et al. Palladium-Catalyzed Formylation of Aryl Halides with tert-Butyl Isocyanide.
Org. Lett. 16, 3492-3495 (2014).
4. 1H and 13C NMR spectra of the isolated products
Figure S2
1H
(top) and 13C (bottom) NMR spectra for benzaldehyde.
Figure S3
1H
(top) and 13C (bottom) NMR spectra for 4-methylbenzaldehyde.
Figure S4 1H (top) and 13C (bottom) NMR spectra for 2-methylbenzaldehyde.
Figure S5
1H
(top) and 13C (bottom) NMR spectra for 3-methylbenzaldehyde.
Figure S6
1H
(top) and 13C (bottom) NMR spectra for 3-methoxylbenzaldehyde.
Figure S7
1H
(top) and 13C (bottom) NMR spectra for 4-methoxylbenzaldehyde.
Figure S8
1H
(top) and 13C (bottom) NMR spectra for 2-methoxylbenzaldehyde.
Figure S9
1H
(top) and 13C (bottom) NMR spectra for 4-isopropylbenzaldehyde.
Figure S10
1H
(top) and 13C (bottom) NMR spectra for 4-chlorobenzaldehyde.
Figure S11
1H
(top) and 13C (bottom) NMR spectra for 4-fluorobenzaldehyde.
Figure S12
1H
(top) and 13C (bottom) NMR spectra for 4-(trifluoromethyl)-benzaldehyde.
Figure S13 1H (top) and 13C (bottom) NMR spectra for 1,4-phthalaldehyde.
Figure S14 1H (top) and 13C (bottom) NMR spectra for terephthaldehyde.
Figure S15
1H
(top) and 13C (bottom) NMR spectra for 1-naphthaldehyde.
Figure S16
1H
(top) and 13C (bottom) NMR spectra for 1-naphthaldehyde.
Figure S17 1H (top) and 13C (bottom) NMR spectra for 3-thiophenecarboxaldehyde.
Figure S18
1H
(top) and 13C (bottom) NMR spectra for 2-thiophenecarboxaldehyde.
Figure S19
1H
(top) and 13C (bottom) NMR spectra for 4-nitrobenzaldehyde.
Figure S20
1H
(top) and 13C (bottom) NMR spectra for 3-pyridinecarboxaldehyde.