Catalysis in polysiloxane gels: Platinum-catalyzed hydrosilylation of polymethylhydrosiloxane leading to reusable catalysts for reduction of nitroarenes

Article abstract of DOI:10.1021/ol9001366

Novel polysiloxane gels, to which platinum species are encapsulated, are prepared by treatment of polymethylhydrosiloxane with alkenes in the presence of Karstedt's catalyst. These gels act as reusable catalysts in the reduction of functionalized nitroarenes with H₂ to the corresponding substituted anilines without leaking the catalyst species.

Full text of DOI:10.1021/ol9001366

Supporting Information for
Catalysis in Polysiloxane Gels: Platinum-Catalyzed Hydrosilylation of
Polymethylhydrosiloxane (PMHS) Leading to Reusable Catalysts for Reduction of
Nitroarenes
Yukihiro Motoyama, Kazuyuki Kamo, and Hideo Nagashima*
Institute for Materials Chemistry and Engineering, Graduate School of Engineering Sciences,
Kyushu University, Kasuga, Fukuoka 816-8580, Japan
*************************************
Contents
1. General Methods
P-S2
P-S2
P-S5
P-S6
P-S7
P-S9
P-S10
P-S12
2. Synthesis of [Pt]@Si Catalysts
3. Synthesis of Nitro Compounds
4. Hydrogenation of Nitro Compounds
5. Spectral Data of Amine Derivatives
6. References
7. NMR Spectra of Nitro Compounds
8. NMR Spectra of Anilines
S 1

1. General Methods
Chemical shifts for 1H NMR are described in parts per million downfield from
tetramethylsilane as an internal standard (δ = 0) in CDCl3 unless otherwise noted. Chemical shifts
for 13C NMR are expressed in parts per million in CDCl3 as an internal standard (δ = 77.1) unless
otherwise noted. ICP-MS analysis was performed at the Analytical Center in Institute for
Materials Chemistry and Engineering, Kyushu University. Analytical thin-layer chromatography
(TLC) was performed on aluminum sheets precoated with aluminum oxide (Merck, aluminum
oxide 150 F254, neutral) and glass plates precoated with silica gel (Merck, Kieselgel 60 F254).
Visualization was accomplished by UV light (254 nm), anisaldehyde, and phosphomolybdic acid.
2. Synthesis of [Pt]@Si Catalysts.
[Pt]@SiO: Prepared by the deoxygenative reduction of N-benzyl-2-pyrrolidinone and PMHS in
the presence of Karstedt’s catalyst according to the method reported previously.1 29Si NMR
(CP/MAS; 5 kHz): δ = 10.1 (Me3SiO–), -35.0 [–OSiHMe(O–)], -56.5 (trisiloxane ring), -64.8
[–OSiMe(O–)2].
[Pt]@SiC6: To a stirred solution of 1,5-hexadiene (180 µL, 1.5 mmol) and PMHS (Mw =
1500–1900; n = 25.6 (average); 140 µL, Si–H = 2 mmol) in tetrahydropyran (0.5 mL) was added
a xylene solution of Karstedt’s catalyst (0.1 M solution, 100 µL, 0.01 mmol). Hydrosilylation
smoothly proceeded and [Pt]@SiC6 was formed as a wet gel within a few minutes. The wet gel
was washed with ether (20 mL) and then dried under reduced pressure to afford the dry gel.
ICP-MS analysis of the ether solution revealed that only 4.6 µg of platinum (<0.24% of charged
Pt species) was contained; >99.76% of Pt species is immobilized into the polysiloxane networks.
IR (KBr): ν = 1259 (Si–Me), 1024 (Si–O) cm-1; 29Si NMR (CP/MAS; 10 kHz): δ = 6.8 (Me3SiO–),
13
-22.8 [CH2SiMe(O-)2]; C NMR (CP/MAS; 10 kHz): δ = 0.5, 18.4, 23.8, 34.0, 115.0, 125.2,
131.9, 139.0.
[Pt]@SiC6-TAA: To a stirred solution of triallylamine (8.7 µL, 0.05 mmol) and PMHS (Mw =
1500–1900; n = 25.6 (average); 140 µL, Si–H = 2 mmol) in tetrahydropyran (0.5 mL) was added
a xylene solution of Karstedt’s catalyst (0.1 M solution, 100 µL, 0.01 mmol). After it was stirred
for 20 min, 1,5-hexadiene (180 µL, 1.5 mmol) was added to the solution. Hydrosilylation
smoothly proceeded and [Pt]@SiC6-TAA was formed as a wet gel within a few minutes. The wet gel
29
was washed with ether (20 mL) and then dried under reduced pressure to afford the dry gel. Si
NMR (CP/MAS; 10 kHz) δ 6.8 (Me3SiO–), -22.6 [CH2SiMe(O-)2], -37.7; 13C NMR (CP/MAS; 10
kHz) δ 0.5, 14.8, 18.3, 23.7, 33.7, 110-140.
S 2

Figure S1. Photos of THP-swelled [Pt]@SiC6 (left) and [Pt]@SiC6-TAA (right).
Figure S2. IR spectra of [Pt]@SiC6 (up) and [Pt]@SiC6-TAA (down).
S 3

[Pt]@SiC6
:
29Si NMR
[Pt]@SiC6:
13C NMR
[Pt]@SiC6-TAA:
13C NMR
[Pt]@SiC6-TAA:
29Si NMR
Figure S3. 29Si NMR (CP/MAS; 10 kHz) and 13C NMR (CP/MAS; 10 kHz) spectra of [Pt]@SiC6
and [Pt]@SiC6-TAA
.
S 4

3. Synthesis of Nitro Compounds. All compounds were identified by spectral comparison with
literature data.
4-Benzyloxynitrobenzene (8e):2 Prepared from 4-hydroxynitrobenzene (1b: 2.78 g, 20 mmol)
and benzyl bromide (3.5 mL, 30 mmol) in a 10:1 mixture of THF and DMF
(totally 33 mL) in the presence of NaH (60 wt%, 1.4 g, 35 mmol); 90% yield;
BnO
NO2
mp: 102.5-103.1 °C; IR (KBr): ν = 2984, 1591, 1509, 1348, 1250, 1174, 1112,
1
1007, 842, 758 cm-1; H NMR (396 MHz, CDCl3): δ = 5.17 (s, 2H), 7.03 (d, J = 9.2 Hz, 2H),
7.33-7.46 (m, 5H), 8.21 (d, J = 9.2 Hz, 2H); 13C NMR (99.5 MHz, CDCl3): δ = 70.7, 114.9, 125.9,
127.5, 128.5, 128.8, 135.5, 141.6, 163.7.
1-(4-Nitrophenyl)ethanol (8f):3 Prepared from 4-nitrophenyl methyl ketone (1d: 1.65 g, 10
mmol) and NaBH4 (444 mg, 12 mmol) in ethanol (20 mL); 72% yield (1.2 g);
IR (neat): ν = 3374, 2976, 1518, 1201, 1089, 1012, 855, 700 cm-1; H NMR
OH
1
(396 MHz, CDCl3): δ = 1.53 (d, J = 6.8 Hz, 3H), 1.92 (d, J = 3.9 Hz, 1H), 5.03
(qd, J = 6.8, 3.9 Hz, 1H), 7.55 (d, J = 8.7 Hz, 2H), 8.21 (d, J = 8.7 Hz, 2H); 13C
NO2
NMR (99.5 MHz, CDCl3): δ = 25.1, 69.1, 123.5, 126.0, 146.7, 153.4.
2-Phenylnitroethane (8h):4 Prepared from β-nitrostyrene, which was obtained by the reaction of
benzaldehyde and nitromethane in MeOH in the presence of NaOH, and NaBH4;
Ph
NO2
83% yield; IR (neat): ν = 3030, 2919, 1555, 1379, 1184, 1083, 862, 752, 700 cm-1;
1H NMR (396 MHz, CDCl3): δ = 3.33 (t, J = 7.5 Hz, 2H), 4.62 (t, J = 7.5 Hz, 2H), 7.21 (d, J = 7.7
13
Hz, 2H), 7.28 (t, J = 7.2 Hz, 1H), 7.34 (dd, J = 7.7, 7.2 Hz, 2H); C NMR (99.5 MHz, CDCl3):
δ = 33.4, 76.2, 127.4, 128.6, 128.9, 135.7.
o-(Methoxycarbonyl)methylnitrobenzene
(10b):5
Prepared
by
esterification
of
o-nitrophenylacetic acid (3.0 g, 16.6 mmol) with MeOH (30 mL) in the
presence of H2SO4; 96% yield (3.1 g); IR (neat): ν = 2954, 1742, 1530, 1436,
CO2Me
NO2
1
1349, 1219, 1171, 1001, 863, 789, 713 cm-1; H NMR (396 MHz, CDCl3): δ =
3.72 (s, 3H), 4.03 (s, 2H), 7.36 (d, J = 7.7 hz, 1H), 7.48 (dd, J = 8.2, 7.2 Hz, 1H), 7.60 (dd, J = 7.7,
7.2 Hz, 1H), 8.12 (d, J = 8.2 Hz, 1H); 13C NMR (99.5 MHz, CDCl3): δ = 39.3, 52.0, 125.1, 128.5,
129.6, 133.3, 133.5, 148.5, 170.3.
S 5

4. Hydrogenation of Nitro Compounds
General Procedure: Hydrogenation of nitro compounds was performed in a 100 mL stainless
autoclave fitted with a glass inner tube, in the presence of nitro compound (1.0 mmol), [Pt]@SiC6
or [Pt]@SiC6-TAA catalyst ([Pt] = 1 mol % for the substrate), and AcOEt (3 mL) at room
temperature or 50 °C under H2 (initial pressure = 10 atm). The insoluble [Pt]@Si catalyst was
removed by filtration with membrane filters (Teflon; 0.45 µm), and the residual gel was washed
with ethyl acetate. The filtrate was concentrated under reduced pressure to give the amine
1
derivatives. The purity and selectivity of the product were determined by capillary GLC and H
NMR analyses.
Gram-Scale Reaction of p-Nitroanisole (1): Hydrogenation was performed in a 100 mL
stainless autoclave fitted with a glass inner tube, in the presence of p-nitroanisole 1 (1.378 g, 9.0
mmol), [Pt]@SiC6 ([Pt] = 1 mol % for 1) and ethyl acetate (10 mL) at room temperature under H2
(initial pressure = 10 atm). After it was stirred for 10 h, the insoluble catalyst was filtered off, and
the filtrate was concentrated under reduced pressure to give p-aminoanisole 2 in 99% yield (1.104
g). Recrystallization from ether/hexane gave 2 in 76% yield.
Recycle Experiments and ICP-MS Analysis of the Product: After the reaction of
p-nitroanisole 1 (1 mmol scale) with [Pt]@SiC6 described as above, the recovered catalyst was
dried under reduced pressure and subjected to a further run of reduction of 1. The platinum
content in p-aminoanisole 2 was determined by ICP-MS analysis: 2 obtained by the above
procedure was dissolved in an aqueous solution of HNO3, and the concentrations of HNO3 were
adjusted to 1.3 x 10-2 wt %. The content of 2 in this solution was 1.0 x 10-2 mol/L. The
measurement was performed using this solution. The platinum content was calibrated with a
commercially available standard reagent (ACROS: platinum atomic absorption standard solution,
1 mg/mL Pt in 10% HCl); five standard solutions, of which Pt concentration is in a range from
10ppb to 200ppb, were used for calibration, and the detection limit was 3ppb.
Reaction of o-(Methoxycarbonyl)methylnitrobenzene (10b). Hydrogenation was performed
in a 100 mL stainless autoclave fitted with a glass inner tube, in the presence of
o-(methoxycarbonyl)methylnitrobenzene 10b (195 mg, 1 mmol), [Pt]@SiC6 ([Pt] = 1 mol % for
10b) and ethyl acetate (3 mL) at room temperature under H2 (initial pressure = 10 atm). After it
was stirred for 24 h, the insoluble catalyst was filtered off, and the filtrate was concentrated under
reduced pressure to give a 3:2 mixture of o-(methoxycarbonyl)methylaniline (12) and oxindole
(13). To a stirred solution of 12 and 13 in ethyl acetate (5 mL) was added 4Å Molecular Sieves
(MS 4A: 2 g). After the resultant suspension was refluxed for 6 h, the insoluble MS 4A was
filtered off, and the filtrate was concentrated under reduced pressure to give oxindole 13 in 99%
yield.
S 6

5. Spectral Data of Amine Derivatives: All compounds were identified by spectral comparison
with samples purchased from commercially sources and literature data.
4-Aminoanisole (2):6,7 mp: 57.8-58.3 °C; IR (KBr): ν = 3427, 3335, 3221, 3073, 3007, 2964,
1
2938, 2912, 1844, 1631, 1499, 1440, 1234, 1129, 1040, 829, 644 cm-1; H
MeO
NMR (396 MHz, CDCl3): δ = 3.42 (bs, 2H), 3.75 (s, 3H), 6.65 (d, J = 8.7 Hz,
NH2
13
2H), 6.75 (d, J = 8.7 Hz, 2H); C NMR (99.5 MHz, CDCl3): δ = 55.7, 114.8,
116.4, 140.0,152.8.
4-Chloroaniline (4a):6 mp: 67.7-68.5 °C; IR (KBr): ν = 3475, 3376, 3201, 1678, 1616, 1506,
1286, 1179, 1083, 1008, 815, 639 cm-1; 1H NMR (396 MHz, CDCl3): δ = 3.65 (bs,
Cl
13
2H), 6.61 (d, J = 8.7 Hz, 2H), 7.10 (d, J = 8.7 Hz, 2H); C NMR (99.5 MHz,
NH2
CDCl3): δ = 116.2, 123.0, 129.1, 145.0; GLC (TC-17, 30 m, detection FID,
column temp. 170 °C), tR = 4.9 min (5), 7.5 min (4a), 8.1 min (3a).
3-Chloroaniline (4b): IR (neat): ν = 3443, 3362, 3214, 3057, 1620, 1597, 1484, 1301, 1266, 1162,
1
1077, 992, 888, 850, 770, 681 cm-1; H NMR (396 MHz, CDCl3): δ = 3.71 (bs, 2H),
Cl
6.54 (ddd, J = 8.2, 2.4, 1.0 Hz, 1H), 6.67 (dd, J = 2.4, 1.9 Hz, 1H), 6.72 (ddd, J = 7.7,
13
NH2
1.9, 1.0 Hz, 1H), 7.06 (dd, J = 8.2, 7.7 Hz, 1H); C NMR (99.5 MHz, CDCl3): δ =
113.1, 114.8, 118.2, 130.3, 134.6, 146.7; GLC (TC-17, 30 m, detection FID, column temp.
150 °C), tR = 5.4 min (5), 10.0 min (4b), 10.5 min (3b).
2-Chloroaniline (4c): IR (neat): ν = 3469, 3379, 3198, 3070, 3025, 1603, 1451, 1306, 1158, 1077,
1023, 835, 678 cm-1; H NMR (396 MHz, CDCl3): δ = 4.03 (bs, 2H), 6.92 (m, 1H),
1
Cl
13
6.77 (dm, J = 7.7 Hz, 1H), 7.07 (m, 1H), 7.24 (dm, J = 8.2 Hz, 1H); C NMR (99.5
NH2
MHz, CDCl3): δ = 115.8, 118.9, 119.2, 127.6, 129.3, 142.9; GLC (TC-17, 30 m,
detection FID, column temp. 170 °C, tR = 4.9 min (5), 6.1 min (4c), 8.3 min (3c).
3-Methoxycarbonyl-4-chloroaniline (7a): IR (neat): ν = 3466, 3376, 3226, 3000, 2951, 2841,
1724, 1626, 1601, 1482, 1440, 1323, 1241, 1121, 1042, 978, 824, 780, 652
Cl
cm-1; 1H NMR (396 MHz, CDCl3): δ = 3.76 (bs, 2H), 3.91 (s, 3H), 6.72 (dd,
MeO2C
NH2
13
J = 8.7, 2.9 Hz, 1H), 7.12 (d, J = 2.9 Hz, 1H), 7.20 (d, J = 8.7 Hz, 1H); C
NMR (99.5 MHz, CDCl3): δ = 52.4, 117.2, 119.1, 122.0, 130.3, 131.6, 145.1, 166.5.
4-Benzyloxy-3-chloroaniline (7b): mp: 56.5-57.5 °C; IR (KBr): ν = 3406, 3299, 3199, 3062,
3032, 2908, 2861, 1628, 1504, 1375, 1269, 1224, 1051, 1010, 915, 852, 739,
BnO
693 cm-1; 1H NMR (396 MHz, CDCl3): δ = 3.48 (bs, 2H), 5.05 (s, 2H), 6.50 (dd,
Cl
NH2
J = 8.7, 2.9 Hz, 1H), 6.76 (d, J = 2.9 Hz, 1H), 6.80 (d, J = 8.7 Hz, 1H), 7.31 (t,
J = 7.2 Hz, 1H), 7.38 (t, J = 7.2 Hz, 2H), 7.45 (d, J = 7.2 Hz, 2H); 13C NMR (99.5 MHz, CDCl3):
S 7

δ = 72.2, 114.2, 117.0, 117.2, 124.4, 127.4, 127.9, 128.5, 137.1, 141.4, 147.1.
2-Chloro-5-aminopyridine (7c): mp: 82.3-83.0 °C; IR (KBr): ν = 3320, 3197, 1573, 1466, 1411,
Cl
1277, 1145, 830 cm-1; 1H NMR (396 MHz, CDCl3): δ = 3.70 (bs, 2H), 6.96 (dd, J
13
= 8.7, 2.9 Hz, 1H), 7.09 (d, J = 8.7 Hz, 1H), 7.85 (d, J = 2.9 Hz, 1H); C NMR
N
NH2
(99.5 MHz, CDCl3): δ = 124.1, 124.8, 136.2, 139.8, 142.0.
4-Aminophenol (9a): mp: 186-188 °C; IR (KBr): ν = 3341, 3281, 3177, 1860, 1615, 1509, 1474,
1
1386, 1092, 970, 826, 750, 646 cm-1; H NMR (396 MHz, [D6]DMSO): δ =
HO
4.34 (bs, 2H), 6.39 (d, J = 8.7 Hz, 2H), 6.46 (d, J = 8.7 Hz, 2H), 8.29 (s, 1H);
13C NMR (99.5 MHz, DMSO-d6): δ = 115.3, 115.6, 140.6, 148.3.
NH2
Ethyl 4-aminobenzoate (9b):7 mp: 91.1-92.3 °C; IR (KBr): ν = 3422, 3342, 3222, 2984, 2957,
2899, 1916, 1683, 1635, 1596, 1513, 1474, 1441, 1367, 1311, 1172, 1109,
O
1
1024, 845, 772, 700 cm-1; H NMR (396 MHz, CDCl3): δ = 1.36 (t, J = 7.2
EtO
Hz, 3H), 4.03 (bs, 2H), 4.32 (q, J = 7.2 Hz, 2H), 6.64(d, J = 8.7 Hz, 2H), 7.86
NH2
13
(d, J = 8.7 Hz, 2H); C NMR (99.5 MHz, CDCl3): δ = 14.4, 60.3, 113.8, 119.9, 131.6, 150.9,
166.8.
4-Aminoacetophenone (9c):6 mp 102.0-102.6 °C; IR (KBr): ν = 3399, 3341, 3301, 2970, 2927,
1
2884, 1614, 1516, 1363, 1260, 1083, 998, 897, 780, 732 cm-1; H NMR (396
O
MHz, CDCl3): δ = 2.50 (s, 3H), 4.11 (bs, 2H), 6.65 (d, J = 8.7 Hz, 2H), 7.80 (d,
13
NH2
J = 8.7 Hz, 2H); C NMR (99.5 MHz, CDCl3): δ = 26.1, 113.7, 127.8, 130.8,
151.3, 196.6.
4-Aminobenzamide (9d): mp 174.8-175.1 °C; IR (KBr) ν 3464, 3327, 3210, 1597, 1518, 1434,
O
1396, 1290, 1095, 851, 779, 712 cm-1; 1H NMR (396 MHz, DMSO-d6) δ 5.57
(bs, 2H), 6.50 (d, J = 8.2 Hz, 2H), 6.79 (bs, 1H), 7.47 (bs, 1H), 7.56 (d, J =
H2N
13
8.2 Hz, 2H); C NMR (99.5 MHz, DMSO-d6) δ 112.5, 121.0, 129.1, 151.7,
NH2
168.1.
4-Benzyloxyaniline (9e):6 mp 45.5-46.0 °C; IR (KBr): ν = 3414, 3375, 3297, 3194, 2907, 2863,
1630, 1589, 1466, 1009, 918, 823, 735, 696 cm-1; 1H NMR (396 MHz, CDCl3):
BnO
δ = 3.43 (bs, 2H), 4.99 (s, 2H), 6.64 (d, J = 8.7 Hz, 2H), 6.81 (d, J = 8.7 Hz,
NH2
13
2H), 7.27-7.45 (m, 5H); C NMR (99.5 MHz, CDCl3): δ = 70.7, 116.1, 116.3,
127.5, 127.8, 128.5, 137.5, 140.3, 151.9.
1-(4-aminophenyl)ethanol (9f):8 mp 59.6-60.2 °C; IR (KBr): ν = 3399, 3341, 3301, 2970, 2927,
1
2884, 1900, 1614, 1516, 1363, 1260, 1083, 1066, 998, 897, 844 cm-1; H NMR (396 MHz,
S 8

OH
CDCl3): δ = 1.47 (d, J = 6.8 Hz, 3H), 3.65 (bs, 2H), 4.80 (q, J = 6.8 Hz, 1H),
13
6.67 (d, J = 8.7 Hz, 2H), 7.17 (d, J = 8.7 Hz, 2H); C NMR (99.5 MHz,
NH2
CDCl3): δ = 24.8, 70.1, 115.1, 126.7, 136.0, 145.8.
3-Aminopyridine (9g): mp 59.7-60.5 °C; IR (KBr): ν = 3376, 3158, 1588, 1488, 1438, 1293,
1261, 708 cm-1; H NMR (396 MHz, CDCl3): δ = 3.64 (bs, 2H), 6.98 (dd, J = 8.2,
1
N
2.9 Hz, 1H), 7.07 (dd, J = 8.2, 4.8 Hz, 1H), 8.02 (d, J = 4.8 Hz, 1H), 8.11 (d, J = 2.9
NH2
Hz, 1H); 13C NMR (99.5 MHz, CDCl3): δ = 121.4, 123.7, 137.4, 139.8, 142.7.
2-Phenylethylamine (9h): IR (neat): ν = 3370, 3025, 2932, 2849, 1602, 1495, 1453, 1079, 838,
746, 700 cm-1; H NMR (396 MHz, CDCl3): δ = 1.21 (bs, 2H), 2.75 (t, J = 6.8 Hz,
2H), 2.97 (t, J = 6.8 Hz, 2H), 7.18-7.33 (m, 5H); 13C NMR (99.5 MHz, CDCl3): δ =
1
Ph
NH2
39.8, 43.2, 125.7, 128.0, 128.4, 139.5.
Indol (11): mp 51.6-52.2 °C; IR (KBr): ν = 3402, 3049, 1455, 1415, 1352, 1336, 1246, 1090, 765
1
cm-1; H NMR (396 MHz, CDCl3): δ = 6.57 (bs, 1H), 7.13 (dd, J = 7.7, 7.2 Hz, 1H),
7.21 (dd, J = 7.7, 7.2 Hz, 1H), 7.22 (bs, 1H), 7.41 (d, J = 7.7 Hz, 1H), 7.66 (d, J = 7.7
Hz, 1H), 8.14 (bs, 1H); 13C NMR (99.5 MHz, CDCl3): δ = 102.4, 111.2, 119.8, 120.7,
N
H
121.9, 124.3, 127.7, 135.7.
Oxindole (13): mp 125.7-126.7 °C; IR (KBr): ν = 3208, 3030, 2949, 1699, 1618, 1471, 1333,
1240, 751 cm-1; 1H NMR (396 MHz, CDCl3): δ = 3.55 (s, 2H), 6.89 (dd, J = 7.2,
O
6.7 Hz, 1H), 7.01 (dd, J = 7.7, 7.2 Hz, 1H), 7.20 (d, J = 6.7 Hz, 1H), 7.23 (d, J =
N
H
7.7 Hz, 1H), 9.12 (bs, 1H); 13C NMR (99.5 MHz, CDCl3): δ = 36.4, 110.0, 122.2,
124.4, 125.3, 127.8, 142.8, 178.8.
6. References
1
2
3
4
Hanada, S.; Motoyama, Y.: Nagashima, H. Tetrahedron Lett. 2006, 47, 6173.
Shintou, T.; Kikuchi, W.; Mukaiyama, T. Bull. Chem. Soc. Jpn. 2003, 76, 1645.
Saito, T.; Nishimoto, Y.; Yasuda, M.; Baba, A. J. Org. Chem. 2006, 71, 8516.
Xue, D.; Chen, Y.-C.; Cui, X.; Wang, Q.-W.; Zhu, J.; Deng, J.-G. J. Org. Chem. 2005, 70,
3584.
5
6
7
8
Salerno, C. P.; Magde, D.; Patron, A. P. J. Org. Chem. 2000, 65, 3971.
Yasuhara, A.; Kasano, A.; Sakamoto, T. J. Org. Chem. 1999, 64, 2301.
Lee, D.-Y.; Hartwig, J. F. Org. Lett. 2005, 7, 1169.
Clerici, A.; Porta, O. J. Org. Chem. 1985, 50, 76.
S 9

7. NMR Spectra of Nitro Compounds
4-Benzyloxynitrobenzene (8e)
BnO
NO2
1-(4-Nitrophenyl)ethanol (8f)
OH
NO2
S 10

2-Phenylnitroethane (8h)
Ph
NO2
o-(Carbomethoxy)methylnitrobenzene (10b)
CO2Me
NO2
S 11

8. NMR Spectra of Anilines
4-Aminoanisole (2)
MeO
NH2
4-Chloroaniline (4a)
Cl
NH2
S 12

3-Chloroaniline (4b):
Cl
NH2
2-Chloroaniline (4c):
Cl
NH2
3-Carbomethoxy-4-chloroaniline (7a)
Cl
MeO2C
NH2
S 13

4-Benzyloxy-3-chloroaniline (7b)
BnO
Cl
NH2
2-Chloro-5-aminopyridine (7c)
Cl
N
NH2
4-Aminophenol (9a)
HO
NH2
S 14

Ethyl 4-aminobenzoate (9b)
O
EtO
NH2
4-Aminoacetophenone (9c)
O
NH2
4-Aminobenzamide (9d)
O
H2N
NH2
S 15

4-Benzyloxyaniline (9e)
BnO
NH2
1-(4-aminophenyl)ethanol (9f)
OH
NH2
3-Aminopyridine (9g)
N
NH2
S 16

2-Phenylethylamine (9h)
Ph
NH2
Indol (11)
N
H
Oxindole (13)
O
N
H
S 17