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Organic & Biomolecular Chemistry
DOI: 10.1039/C7OB00374A
ARTICLE
Journal Name
1
3
C
CAL-B (12.5 mg) were added over a solution of the corresponding (dd, J = 8.0, 1.6 Hz, 1H), 6.83 (d, J = 8.0 Hz, 1H), 6.00 (s, 2H).
amine 1a-t (0.5 mmol) in EtOAc (1 mL). The suspension was shaken NMR (75 MHz, CDCl ): δ (ppm) 149.9 (CH), 149.3 (C), 148.2 (C),
for 1 h at 30 °C and 250 rpm. After this time the reaction was 126.2 (C), 108.3 (CH), 105.6 (CH), 101.4 (CH ).
stopped by addition of water (1 mL) and the enzyme filtered off. (E)-4-Methoxybenzaldehyde oxime (2i). Yield (71%, 53.7 mg R
3
2
(20%
The solution was extracted with EtOAc (3 × 1 mL). An aliquot of the EtOAc/ Hexane) 0.56. Brown solid.). H NMR (300 MHz, CDCl ): δ
organic phase was taken for GC analyses. The resulting organic (ppm) 8.12 (s, 1H), 7.54-7.51 (d, J = 8.8 Hz, 2H), 6.93-6.90 (d, J = 8.8
f
1
3
1
3
phase was dried over Na
evaporated under reduced pressure to obtain the corresponding 149.7 (CH), 128.5 (CH), 124.6 (C), 114.1 (CH), 55.3 (CH
E)-oximes 2a-t. For aldoximes 2a-k a column chromatography on (E)-3-Methoxybenzaldehyde oxime (2j). Yield (82%, 62.0 mg). R
2
SO
4
, filtered and the solvent was Hz, 2H), 3.84 (s, 3H). C NMR (75 MHz, CDCl
3
): δ (ppm) 161.0 (C),
3
).
(
f
1
silica gel (20% EtOAc/hexane) was necessary to achieve the final (20% EtOAc/ Hexane) 0.54. Brown solid. H NMR (300 MHz, CDCl
products in high purity.
E)-Benzaldehyde oxime (2a). Yield (80%, 48.5 mg). R
3
):
δ (ppm) 8.15 (s, 1H), 7.35-7.30 (m, 1H), 7.19-7.13 (m, 2H), 6.98-6.96
1
3
(
3
m, 1H), 3.85 (s, 3H). C NMR (75 MHz, CDCl ): δ (ppm) 157.6 (C),
(
f
(20% EtOAc/
1
146.6 (CH), 131.1 (CH), 127.3 (CH), 120.7 (CH), 120.6 (C), 111.1 (CH),
Hexane) 0.61. White solid. mp: 32-33 °C. H NMR (300 MHz, CDCl ):
3
1
3
55.5 (CH3).
δ (ppm) 8.24 (s, 1H), 7.65-7.62 (m, 2H), 7.44-7.42 (m, 3H). C NMR
(
(
E)-2-Methoxybenzaldehyde oxime (2k). Yield (80%, 60.5 mg). R
f
(
(
(
3
75 MHz, CDCl ): δ (ppm) 150.5 (CH), 131.8 (C), 130.1 (CH), 128.8
1
3
20% EtOAc/ Hexane) 0.58. Brown solid. H NMR (300 MHz, CDCl ):
CH), 127.1 (CH).
δ (ppm) 8.15 (s, 1H), 7.35-7.30 (m, 1H), 7.16-7.12 (m, 2H), 6.98-6.95
E)-4-Methylbenzaldehyde oxime (2b). Yield (78%, 52.7 mg). R
f
(20%
): δ
13
1
(m, 1H), 3.85 (s, 3H). C NMR (75 MHz, CDCl
50.1 (CH), 133.2 (C), 129.8 (CH), 120.0 (CH), 116.4 (CH), 111.2 (CH),
55.3 (CH3).
E)-Acetophenone oxime (2l). Yield (96%, 64.9 mg). R
3
): δ (ppm) 159.8 (C),
EtOAc/ Hexane) 0.60. White solid. H NMR (300 MHz, CDCl
3
1
(
ppm) 8.15 (s, 1H), 7.50 (d, J = 8.0 Hz, 2H), 7.21 (d, J = 8.0 Hz, 2H),
1
3
2
.39 (s, 3H). C NMR (75 MHz, CDCl
3
): δ (ppm) 150.2 (CH), 140.3
).
(
f
(20% EtOAc/
): δ (ppm) 7.67-
7.64 (m, 2H), 7.42-7.40 (m, 3H), 2.33 (s, 3H). C NMR (75 MHz,
CDCl ): δ (ppm) 156.0 (C), 136.5 (C), 129.2 (CH), 128.5 (CH), 126.0
(CH), 12.2 (CH ).
E)-1-(p-Tolyl)ethanone oxime (2m) Yield (90%, 67.1 mg). R (20%
(
C), 129.5 (CH), 129.2 (C), 126.9 (CH), 21.5 (CH
3
1
Hexane) 0.61. White solid. H NMR (300 MHz, CDCl
3
(
E)-4-Chlorobenzaldehyde oxime (2c). Yield (82%, 63.8 mg). R (20%
f
1
3
1
EtOAc/ Hexane) 0.52. White solid. H NMR (300 MHz, CDCl
3
): δ
3
(
ppm) 8.53 (s, 1H), 8.13 (s, 1H), 7.52 (d, J = 5.0, 2H), 7.36 (d, J = 5.0,
1
3
3
2
3
H). C NMR (75 MHz, CDCl ): δ (ppm) 149.2 (CH), 135.9 (C), 130.5
(
f
(
C), 129.0 (CH), 128.1 (CH).
E)-4-Fluorobenzaldehyde oxime (2d). Yield (80%, 55.7 mg). R
1
EtOAc/ Hexane) 0.59. White solid. H NMR (300 MHz, CDCl
3
): δ
(
f
(20%
): δ
ppm) 8.25 (s, 1H), 8.15 (s, 1H), 7.59 (dd, J =8.5, 5.5 Hz, 2H), 7.10 (t,
1
(ppm) 7.55 (d, J = 8.0 Hz, 2H), 7.22 (d, J = 8.0 Hz, 2H), 2.40 (s, 3H),
EtOAc/ Hexane) 0.54. White solid. H NMR (300 MHz, CDCl
3
1
3
2
.32 (s, 3H). C NMR (75 MHz, CDCl
3
): δ (ppm) 155.9 (C), 139.3 (C),
(
1
3
133.6 (C), 129.2 (CH), 125.9 (CH), 21.3 (CH ), 12.3 (CH ).
3
3
J = 8.5 Hz, 2H). C NMR (75 MHz, CDCl
Hz, C), 149.2 (CH), 128.8 (d, J = 8.5 Hz, CH), 128.2 (C), 116.1 (d, J =
2.0 Hz, CH).
E)-4-(tert-Butyl)benzaldehyde oxime (2e). Yield (74%, 65.6 mg). R
3
): δ (ppm) 163.5 (d, J = 250
(
(
E)-1-(4-Chlorophenyl)ethanone oxime (2n). Yield (95%, 80.6 mg). R
f
1
3
20% EtOAc/ Hexane) 0.55. White solid. H NMR (300 MHz, CDCl ):
2
δ (ppm) 7.58 (d, J = 8.8 Hz, 2H), 7.37 (d, J = 8.8 Hz, 2H), 2.30 (s, 3H).
(
(
f
1
3
1
3
C NMR (75 MHz, CDCl ): δ (ppm) 155.1 (C), 135.3 (C), 134.9 (C),
3
20% EtOAc/ Hexane) 0.50. White solid. H NMR (300 MHz, CDCl ):
1
28.7 (CH), 127.3 (CH), 12.1 (CH
3
).
δ (ppm) 8.16 (s, 1H), 7.53 (d, J = 8.5 Hz, 2H), 7.43 (d, J = 8.5 Hz, 2H),
1
3
(E)-1-(4-Fluorophenyl)ethanone oxime (2o). Yield (98%, 75.0 mg). Rf
1
.35 (s, 9H). C NMR (75 MHz, CDCl
CH), 129.1 (C), 126.8 (CH), 125.7 (CH), 34.8 (C), 31.2 (CH
E)-4-(Trifluoromethyl)benzaldehyde oxime (2f). Yield (78%, 73.8
3
): δ (ppm) 153.4 (C), 150.1
1
(
20% EtOAc/ Hexane) 0.57. White solid. H NMR (300 MHz, CDCl
3
):
(
(
3
).
δ (ppm) 7.63 (dd, J = 9.0, 5.3 Hz, 2H), 7.09 (t, J = 9.0, 2H), 2.31 (s,
1
3
1
3H). C NMR (75 MHz, CDCl ): δ (ppm) 163.4 (d, J = 250 Hz, C),
3
mg). R
CDCl ): δ (ppm) 8.77 (br s, 1H), 8.21 (s, 1H), 7.75-7.63 (m, 4H).
NMR (75 MHz, CDCl ): δ (ppm) 149.2 (CH), 135.2 (C), 131.8 (q, J =
f
(20% EtOAc/ Hexane) 0.62. White solid. H NMR (300 MHz,
1
3
155.1 (C), 132.6 (C), 127.9 (d, J = 8.7 Hz, CH), 115.5 (d, J = 21.7 Hz,
3
C
CH), 12.3 (CH
3
).
3
(
E)-1-[4-(Trifluoromethyl)phenyl]ethanone oxime (2p). Yield (96%,
3
2.8 Hz, C), 127.2 (CH), 125.7 (q, J = 3.7 Hz, C), 123.8 (q, J = 272 Hz,
1
19
97.5 mg). R (20% EtOAc/ Hexane) 0.60. White solid. H NMR (300
f
C). F NMR (282 MHz, CDCl
3
): δ (ppm) 63.2.
MHz, CDCl ): δ (ppm) 7.76 (d, J = 8.2 Hz, 2H), 7.66 (d, J = 8.2 Hz, 2H),
3
(
E)-3-(Trifluoromethyl)benzaldehyde oxime (2g). Yield (79%, 74.7
13
1
3
2.34 (s, 3H). C NMR (75 MHz, CDCl ): δ (ppm) 155.1 (C), 139.8 (C),
f
mg). R (20% EtOAc/ Hexane) 0.61. Yellow solid. H NMR (300 MHz,
1
31.1 (q, J = 32.7 Hz, C), 126.3 (CH), 125.5 (q, J = 3.7 Hz, CH), 123.9
(q, J = 272.3 Hz, C), 12.2 (CH3).
E)-1-[3-(Trifluoromethyl)phenyl]ethanone oxime (2q). Yield (91%,
CDCl
Hz, 1H), 7.67 (d, J = 7.8 Hz, 1H), 7.53 (t, J = 7.8 Hz, 1H). C NMR (75
MHz, CDCl ): δ (ppm) 149.0 (CH), 132.7 (C), 131.3 (q, J = 32.7 Hz, C),
30.0 (CH), 129.3 (CH), 126.6 (q, J = 3.8 Hz, CH) , 123.8 (q, J = 3.8 Hz,
3
): δ (ppm) 8.94 (s, 1H), 8.24 (s, 1H), 7.87 (s, 1H), 7.78 (d, J = 7.8
1
3
(
3
1
9
2.4 mg). R
f
(20% EtOAc/ Hexane) 0.62. White solid. H NMR (300
1
19
MHz, CDCl ): δ (ppm) 7.91 (s, 1H), 7.83 (d, J = 7.8 Hz, 1H), 7.66 (d, J
3
CH), 123.7 (q, J = 272 Hz, C). F NMR (282 MHz, CDCl
2.5.
E)-Benzo[d][1,3]dioxole-5-carbaldehyde oxime (2h). Yield (73%,
3
): δ (ppm)
1
3
=
7.8 Hz, 1H), 7.54 (t, J = 7.8 Hz, 1H), 2.34 (s, 3H). C NMR (75 MHz,
CDCl ): δ (ppm) 154.9 (C), 137.3 (C), 130.9 (q, J = 32.4 Hz), 129.2
(CH), 129.0 (CH), 125.8 (q, J = 3.8 Hz, CH), 124.3 (q, J = 273 Hz, C),
6
3
(
1
6
0.6 mg R
f
(20% EtOAc/ Hexane) 0.40. Yellow solid.). H NMR (300
1
22.9 (C), 12.0 (CH
3
).
MHz, CDCl ): δ (ppm) δ 8.06 (s, 1H), 7.19 (d, J = 1.6 Hz, 1H), 6.98
3
4
| Organic & Biomolecular Chemistry., 2017, 00, 1-5
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