Molecules 2019, 24, 4122
11 of 14
1
R = 0.33 (c-Hex/EtOAc = 5:1). H-NMR (300 MHz, CDCl )
δ
/ppm = 7.31–7.16 (m, 5H, CH Ph),
f
3
2
7
5
.15–7.02 (m, 2H, 2
×
C H), 6.73 (tt, J = 7.3, 1.1 Hz, 1H, C H), 6.63 (dd, J = 8.6, 1.2 Hz, 2H, 2
×
C H),
Ar
Ar
Ar
.07 (s, 2H, CH Ph), 4.14 (q, J = 7.0 Hz, 1H, CHN), 3.98 (s, 1H, NH), 1.42 (d, J = 7.0 Hz, 3H, CHCH ).
2
3
The analytical data matches the data reported in the literature [24].
Benzyl (2-methoxyphenyl)alaninate (7d)
GP was followed by adding benzyl 2-diazopropanoate (19.0 mg, 1.00 mmol, 1.00 equiv.) and
o-anisidine (14.8 mg, 1.20 mmol, 1.20 equiv.) to a suspension of in situ generated Cu-(R ,S)-4a catalyst.
The product was obtained via column chromatography (c-Hex/EtOAc = 5:1) as a light-yellow solid,
p
2
3.3 mg, 0.82 mmol, 82%.
1
H-NMR (300 MHz, CDCl3)
δ
/ppm = 7.40–7.06 (m, 5H, CH Ph), 6.78–6.66 (m, 2H, 2
×
C H), 6.62
Ar
2
(
1
ddd, J = 8.2, 7.2, 1.6 Hz, 1H, C H), 6.44 (dd, J = 7.6, 1.6 Hz, 1H, C H), 5.07 (s, 2H, CH Ph), 4.64 (s,
Ar Ar 2
13
H, NH), 4.12 (q, J = 7.0 Hz, 1H, CHN), 3.76 (s, 3H, OCH ), 1.44 (d, J = 6.9 Hz, 3H, CHCH ). C-NMR
3
3
(
75 MHz, CDCl3)
δ
/ppm = 174.5 (C
CAr), 128.3 (+, CH, CAr), 128.2 (+, CH, 2
, CH , CH Ph), 55.5(+, CH , OCH ), 52.0(+, CH, CHN), 18.9
q
, CO Bn), 147.2 (C
q
, CAr), 136.6 (C
q
, CAr), 135.8 (C
q
, CAr), 128.6 (+,
2
CH, 2
(
(
×
×
CAr), 121.3 (+, CH, CAr), 117.7 (+, CH, CAr), 110.6
+, CH, C ), 109.9 (+, CH, C ), 66.8 (
−
Ar
Ar
2
2
3
3
+, CH3).
The analytical data matches the data reported in the literature [24].
Benzyl (3-Methoxyphenyl)alaninate (7e)
GP was followed by adding benzyl 2-diazopropanoate (19.0 mg, 1.00 mmol, 1.00 equiv.) and
m-anisidine (14.8 mg, 1.20 mmol, 1.20 equiv.) to a suspension of in situ generated Cu-(R ,S)-4a catalyst.
p
The product was obtained via column chromatography (c-Hex/EtOAc = 5:1) as light-yellow solid, 15.1
mg, 53%.
1H-NMR (300 MHz, CDCl3)
δ/ppm = 7.39–7.27 (m, 5H, CH Ph), 7.07 (t, J = 8.1 Hz, 1H, C H),
2 Ar
6
.32 (dd, J = 8.2, 2.3 Hz, 1H, CArH), 6.25–6.19 (m, 1H, CArH), 6.16 (t, J = 2.3 Hz, 1H, CArH), 5.16 (s, 2H,
13
CH Ph), 4.19 (q, J = 6.9 Hz, 1H, CHN), 3.74 (s, 1H, NH), 1.48 (d, J = 6.9 Hz, 3H, CHCH ). C-NMR (75
2
3
MHz, CDCl3)
δ/ppm = 174.3 (C
q
, CO Bn), 160.8 (C
q
, C ), 147.9 (C
q
, C ), 135.5 (C
q
, C ), 130.1 (+, CH,
2
Ar
Ar
Ar
C ), 128.5 (+, CH, 2
×
C ), 128.3 (+, CH, C ), 128.1 (+, CH, 2
×
C ), 106.3 (+, CH, C ), 103.7 (+, CH,
Ar Ar
Ar
Ar
Ar
C ), 99.5 (+, CH, C ), 66.8 ( , CH , CH Ph), 55.0 (+, CH , OCH ), 52.0 (+, CH, CHN), 18.8 (+, CH ).
−
Ar
Ar
2 2 3 3 3
Benzyl (4-methoxyphenyl)alaninate (7f)
GP was followed by adding benzyl 2-diazopropanoate (19.0 mg, 1.00 mmol, 1.00 equiv.) and
p-anisidine (14.8 mg, 1.20 mmol, 1.20 equiv.) to a suspension of in situ generated Cu-(R ,S)-4a catalyst.
p
The product was obtained via column chromatography (c-Hex/EtOAc = 4:1) as light-yellow solid, 20.0
mg, 70%.
1H-NMR (300 MHz, CDCl3)
δ
/ppm = 7.38–7.03 (m, 5H, CH Ph), 6.72–6.61 (m, 2H, 2
×
C H), 6.51
Ar
2
(
d, J = 9.0 Hz, 2H, 2
×
C H), 5.06 (s, 2H, CH Ph), 4.04 (q, J = 6.9 Hz, 1H, CHN), 3.66 (s, 3H, CH ).
Ar 2 3
1
3
C-NMR (75 MHz, CDCl )
δ/ppm = 175.3 (C
q
, CO Bn), 153.4 (C
q
, CAr), 141.2 89 (C
q
, CAr), 136.1 (C
q
,
3
2
C ), 129.1 (+, CH, 2
×
C ), 128.8 (+, CH, C ), 128.6 (+, CH, 2
×
C ), 115.7 (+, CH, 2
×
C ), 115.4 (+,
Ar
Ar
Ar
Ar
Ar
CH, 2 × C ), 67.2 (−, CH , CH Ph), 56.2 (+, CH OCH ,), 53.8 (+, CH, CHN), 19.5 (+, CH ).
Ar
2
2
3
3
3
The analytical data matches the data reported in the literature[25].
Benzyl o-tolylalaninate (7g)
GP was followed by adding benzyl 2-diazopropanoate (19.0 mg, 1.00 mmol, 1.00 equiv.) and
o-toluidine (12.9 mg, 1.20 mmol, 1.20 equiv.) to a suspension of in situ generated Cu-(R ,S)-4a catalyst.
The product was obtained via column chromatography (c-Hex/EtOAc = 5:1) as colorless solid, 18.3 mg,
p
0
.68 mmol, 68%.
1H-NMR (300 MHz, CDCl3)
δ/ppm = 7.44–7.27 (m, 5H, CH Ph), 7.15–7.05 (m, 2H, Ph), 6.72 (td,
2
J = 7.4, 1.2 Hz, 1H, Ph), 6.55 (dd, J = 8.4, 1.2 Hz, 1H, Ph), 5.19 (s, 2H, CH Ph), 4.27 (q, J = 6.9 Hz, 1H,
2
13
CHCH ), 4.08 (s, 1H, NH), 2.21 (s, 3H, CH ), 1.55 (d, J = 6.9 Hz, 3H, CHCH ). C-NMR (75 MHz,
3
3
3