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O. K. ARJOMANDI ET AL.
(CH3O), 37.4 (CH2CHNH), 28.3 (C(CH3)3). HRMS calculated for (S)-Methyl
C22H26N2NaO7 [M þ Na]þ 453.1632, found 453.1635.
2-amino-3-(4-((3-nitrobenzyl)oxy)phenyl)propanoate
(6h). Brown solid, 1.62 g (98%). 1H NMR (400 MHz, CDCl3): d 8.26
(1H, s, Ar-H), 8.12 (1H, d, J ¼ 8.2 Hz, Ar-H), 7.72 (1H, d, J ¼ 7.6 Hz,
Ar-H), 7.52 (1H, t, J ¼ 7.9 Hz, Ar-H), 7.09 (2H, d, J ¼ 8.5 Hz, Ar-H),
6.87 (2H, d, J ¼ 8.5 Hz, Ar-H), 5.08 (2H, s, CH2O), 3.72 (1H, dd,
J ¼ 7.4, 5.1 Hz, CH2CHNH), 3.67 (3H, s, CH3O), 3.02 (1H, dd, J ¼ 13.6,
5.1 Hz, CHAHBCHNH), 2.84 (1H, dd, J ¼ 13.7, 7.7 Hz, CHAHBCHNH),
2.75 (2H, bs, NH2). 13 C NMR (100 MHz, CDCl3): d 174.5 (CO), 157.1
(Ar-C), 148.3 (Ar-C), 139.1 (Ar-C), 133.0 (Ar-C), 130.4 (Ar-C), 129.5
(Ar-C), 122.8 (Ar-C), 122.0 (Ar-C), 121.2 (Ar-C), 114.8 (Ar-C), 68.5
(CH2O), 55.4 (CH2CHNH), 52.0 (CH3O), 39.3 (CH2CHNH). HRMS cal-
culated for C17H19N2O5 [M þ H]þ 331.1288, found 331.1286.
(S)-Methyl
2-amino-3-(4-((2-nitrobenzyl)oxy)phenyl)propanoate
(6g). Tan yellow viscous oil, 1.62 g (98%). 1H NMR (500 MHz,
CDCl3): d 8.13 (1H, d, J ¼ 8.0 Hz, Ar-H), 7.86 (1H, d, J ¼ 7.8 Hz, Ar-H),
7.65 (1H, t, J ¼ 7.6 Hz, Ar-H), 7.46 (1H, t, J ¼ 8.0 Hz, Ar-H), 7.10 (2H,
d, J ¼ 8.5 Hz, Ar-H), 6.90 (2H, d, J ¼ 8.5 Hz, Ar-H), 5.44 (2H, s, CH2O),
3.69 (4H, s: 1H for CH2CHNH and 3H for CH3O), 3.01 (1H, dd,
J ¼ 13.6, 5.1 Hz, CHAHBCHNH), 2.82 (1H, dd, J ¼ 13.7, 7.7 Hz,
CHAHBCHNH), 1.95 (2H, bs, NH2). 13 C NMR (125 MHz, CDCl3): d
175.2 (CO), 157.1 (Ar-C), 146.9 (Ar-C), 134.0 (Ar-C), 133.9 (Ar-C),
130.4 (Ar-C), 129.9 (Ar-C), 128.5 (Ar-C), 128.3 (Ar-C), 124.9 (Ar-C),
115.0 (Ar-C), 66.8 (CH2O), 55.7 (CH2CHNH), 52.0 (CH3O), 39.9
(CH2CHNH). HRMS calculated for C17H19N2O5 [M þ H]þ 331.1288,
found 331.1290.
(S)-Methyl 2-(2-(acetylthio)acetamido)-3-(4-((3-nitrobenzyl)oxy)phe-
nyl)propanoate (8h). Yellow solid, 1.45 g (81%). H NMR (400 MHz,
1
CDCl3): d 8.28 (1H, s, Ar-H), 8.15 (1H, d, J ¼ 8.2 Hz, Ar-H), 7.73 (1H,
d, J ¼ 7.6 Hz, Ar-H), 7.54 (1H, t, J ¼ 7.9 Hz, Ar-H), 7.00 (2H, d,
J ¼ 8.5 Hz, Ar-H), 6.88 (2H, d, J ¼ 8.5 Hz, Ar-H), 6.62 (1H, d,
J ¼ 7.6 Hz, NH), 5.10 (2H, s, CH2O), 4.74 (1H, dt, J ¼ 7.8, 5.8 Hz,
CH2CHNH), 3.69 (3H, s, CH3O), 3.51 (2H, dd, J ¼ 22.8, 14.9 Hz,
CH2S), 3.07 (1H, dd, J ¼ 13.8, 5.5 Hz, CHAHBCHNH), 2.98 (1H, dd,
J ¼ 13.8, 6.1 Hz, CHAHBCHNH), 2.33 (3H, s, CH3CO). 13 C NMR
(100 MHz, CDCl3): d 195.2 (COS), 171.5 (CO2), 167.6 (CONH), 157.3
(Ar-C), 148.4 (Ar-C), 139.1 (Ar-C), 133.1 (Ar-C), 130.5 (Ar-C), 129.5
(Ar-C), 128.6 (Ar-C), 122.9 (Ar-C), 122.1 (Ar-C), 114.8 (Ar-C), 68.6
(CH2O), 53.5 (CH2CHNH), 52.4 (CH3O), 36.8 (CH2CHNH), 32.7 (CH2S),
30.1 (CH3CO). HRMS calculated for C21H22N2NaO7S [M þ Na]þ
469.1040, found 469.1045.
(S)-Methyl 2-(2-(acetylthio)acetamido)-3-(4-((2-nitrobenzyl)oxy)phe-
nyl)propanoate (8g). Pale yellow solid, 1.48 g (83%). 1H NMR
(500 MHz, CDCl3): d 8.13 (1H, d, J ¼ 8.0 Hz, Ar-H), 7.86 (1H, d,
J ¼ 7.8 Hz, Ar-H), 7.66 (1H, t, J ¼ 7.6 Hz, Ar-H), 7.47 (1H, t, J ¼ 8.0 Hz,
Ar-H), 7.00 (2H, d, J ¼ 8.5 Hz, Ar-H), 6.88 (2H, d, J ¼ 8.5 Hz, Ar-H),
6.59 (1H, d, J ¼ 7.6 Hz, NH), 5.43 (2H, s, CH2O), 4.76 (1H, dt, J ¼ 7.8,
5.8 Hz, CH2CHNH), 3.70 (3H, s, CH3O), 3.51 (2H, dd, J ¼ 28.2,
15.0 Hz, CH2S), 3.08 (1H, dd, J ¼ 13.8, 5.5 Hz, CHAHBCHNH), 2.99
(1H, dd, J ¼ 13.8, 6.1 Hz, CHAHBCHNH), 2.33 (3H, s, CH3CO). 13 C
NMR (125 MHz, CDCl3): d 195.2 (COS), 171.5 (CO2), 167.6 (CONH),
157.3 (Ar-C), 146.9 (Ar-C), 134.0 (Ar-C), 133.8 (Ar-C), 130.5 (Ar-C),
128.5 (Ar-C), 128.5 (Ar-C), 128.3 (Ar-C), 125.0 (Ar-C), 114.9 (Ar-C),
66.8 (CH2O), 53.5 (CH2CHNH), 52.4 (CH3O), 36.8 (CH2CHNH), 32.8
(CH2S), 30.2 (CH3CO). HRMS calculated for C21H22N2NaO7S
[M þ Na]þ 469.1040, found 469.1045.
(S)-2-(2-Mercaptoacetamido)-3-(4-((3-nitrobenzyl)oxy)phenyl)pro-
panoic acid (2h). Pale yellow solid, 0.82 g (70%). 1H NMR
(400 MHz, CDCl3): d 10.56 (1H, bs, OH), 8.25 (1H, s, Ar-H), 8.13 (1H,
d, J ¼ 8.2 Hz, Ar-H), 7.71 (1H, d, J ¼ 7.6 Hz, Ar-H), 7.52 (1H, t,
J ¼ 7.9 Hz, Ar-H), 7.20 (1H, d, J ¼ 7.8 Hz, NH), 7.09 (2H, d, J ¼ 8.5 Hz,
Ar-H), 6.88 (2H, d, J ¼ 8.5 Hz, Ar-H), 5.07 (2H, s, CH2O), 4.80 (1H, dt,
J ¼ 7.8, 5.2 Hz, CH2CHNH), 3.20 (2H, d, J ¼ 9.1 Hz, CH2SH), 3.16 (1H,
dd, J ¼ 13.8, 5.5 Hz, CHAHBCHNH), 3.07 (1H, dd, J ¼ 13.8, 6.1 Hz,
CHAHBCHNH), 1.84 (3H, t, J ¼ 9.1 Hz, SH). 13 C NMR (100 MHz,
CDCl3): d 174.8 (CO2H), 170.3 (CONH), 157.4 (Ar-C), 148.3 (Ar-C),
139.0 (Ar-C), 133.1 (Ar-C), 130.5 (Ar-C), 129.5 (Ar-C), 128.2 (Ar-C),
122.9 (Ar-C), 122.1 (Ar-C), 114.9 (Ar-C), 68.5 (PhCH2O), 53.5
(CH2CHNH), 36.3 (CH2CHNH), 28.0 (CH2SH). HRMS calculated for
C18H17N2O6S [M-H]ꢀ 389.0813, found 389.0805.
(S)-2-(2-Mercaptoacetamido)-3-(4-((2-nitrobenzyl)oxy)phenyl)pro-
panoic acid (2g). Pale yellow solid, 0.79 g (67%). 1H NMR
(500 MHz, CDCl3): d 8.22 (1H, bs, OH), 8.12 (1H, d, J ¼ 8.0 Hz, Ar-H),
7.84 (1H, d, J ¼ 7.8 Hz, Ar-H), 7.64 (1H, t, J ¼ 7.6 Hz, Ar-H), 7.45 (1H,
t, J ¼ 8.0 Hz, Ar-H), 7.13 (1H, d, J ¼ 7.6 Hz, NH), 7.00 (2H, d,
J ¼ 8.5 Hz, Ar-H), 6.89 (2H, d, J ¼ 8.5 Hz, Ar-H), 5.41 (2H, s, CH2O),
4.80 (1H, q, J ¼ 6.4 Hz, CH2CHNH), 3.20 (2H, d, J ¼ 9.1 Hz, CH2SH),
3.16 (1H, dd, J ¼ 13.8, 5.5 Hz, CHAHBCHNH), 3.07 (1H, dd, J ¼ 13.8,
6.1 Hz, CHAHBCHNH), 1.83 (3H, t, J ¼ 9.1 Hz, SH). 13 C NMR
(125 MHz, CDCl3): d 177.0 (CO2H), 170.0 (CONH), 157.4 (Ar-C), 146.9
(Ar-C), 134.0 (Ar-C), 133.7 (Ar-C), 130.6 (Ar-C), 128.5 (Ar-C), 128.3
(Ar-C), 128.3 (Ar-C), 124.9 (Ar-C), 115.1 (Ar-C), 66.8 (PhCH2O), 53.5
(CH2CHNH), 36.4 (CH2CHNH), 28.1 (CH2SH). HRMS calculated for
C18H17N2O6S [M-H]ꢀ 389.0813, found 389.0809.
(S)-Methyl 2-((tert-butoxycarbonyl)amino)-3-(4-((4-nitrobenzyl)oxy)-
phenyl)propanoate (5i). Brown viscous oil, 2.69 g (92%). 1H NMR
(500 MHz, CDCl3): d 8.21 (2H, d, J ¼ 8.7 Hz, Ar-H), 7.56 (2H, d,
J ¼ 8.7 Hz, Ar-H), 7.03 (2H, d, J ¼ 8.5 Hz, Ar-H), 6.86 (2H, d,
J ¼ 8.5 Hz, Ar-H), 5.12 (2H, s, CH2O), 4.96 (1H, d, J ¼ 7.3 Hz, NH),
4.50 (1H, q, J ¼ 7.6 Hz, CH2CHNH), 3.68 (3H, s, CH3O), 3.03 (1H, dd,
J ¼ 13.8, 5.8 Hz, CHAHBCHNH), 2.97 (1H, dd, J ¼ 13.8, 6.0 Hz,
CHAHBCHNH), 1.38 (9H, s, C(CH3)3). 13 C NMR (125 MHz, CDCl3): d
172.3 (CO2CH3), 157.2 (NHCO2), 155.0 (Ar-C), 147.5 (Ar-C), 144.5
(Ar-C), 130.4 (Ar-C), 129.0 (Ar-C), 127.5 (Ar-C), 123.8 (Ar-C), 114.8
(Ar-C), 79.9 (C(CH3)3), 68.6 (CH2O), 54.5 (CH2CHNH), 52.2 (CH3O),
37.4 (CH2CHNH), 28.2 (C(CH3)3). HRMS calculated for C22H26N2NaO7
[M þ Na]þ 453.1632, found 453.1636.
(S)-Methyl 2-((tert-butoxycarbonyl)amino)-3-(4-((3-nitrobenzyl)oxy)-
phenyl)propanoate (5h). Yellow viscous oil, 2.63 g (90%). 1H NMR
(500 MHz, CDCl3): d 8.27 (1H, s, Ar-H), 8.15 (1H, d, J ¼ 8.2 Hz, Ar-H),
7.72 (1H, d, J ¼ 7.6 Hz, Ar-H), 7.52 (1H, t, J ¼ 7.9 Hz, Ar-H), 7.03 (2H,
d, J ¼ 8.5 Hz, Ar-H), 6.86 (2H, d, J ¼ 8.5 Hz, Ar-H), 5.09 (2H, s, CH2O),
4.98 (1H, d, J ¼ 7.9 Hz, NH), 4.51 (1H, q, J ¼ 7.0 Hz, CH2CHNH), 3.67
(3H, s, CH3O), 3.03 (1H, dd, J ¼ 13.8, 5.8 Hz, CHAHBCHNH), 2.96 (1H,
dd, J ¼ 13.8, 6.0 Hz, CHAHBCHNH), 1.38 (9H, s, C(CH3)3). 13 C NMR
(125 MHz, CDCl3): d 172.3 (CO2CH3), 157.2 (NHCO2), 155.0 (Ar-C),
148.3 (Ar-C), 139.2 (Ar-C), 133.0 (Ar-C), 130.4 (Ar-C), 129.5 (Ar-C),
128.9 (Ar-C), 122.8 (Ar-C), 122.0 (Ar-C), 114.8 (Ar-C), 79.8 (C(CH3)3),
(S)-Methyl
2-amino-3-(4-((4-nitrobenzyl)oxy)phenyl)propanoate
68.5 (CH2O), 54.4 (CH2CHNH), 52.1 (CH3O), 37.4 (CH2CHNH), 28.2 (6i). Dark brown solid, 1.62 g (98%). 1H NMR (400 MHz, CDCl3): d
(C(CH3)3). HRMS calculated for C22H26N2NaO7 [M þ Na]þ 453.1632, 8.16 (2H, d, J ¼ 8.7 Hz, Ar-H), 7.80 (2H, bs, NH2), 7.53 (2H, d,
found 453.1639.
J ¼ 8.7 Hz, Ar-H), 7.08 (2H, d, J ¼ 8.5 Hz, Ar-H), 6.87 (2H, d,