Page 5 of 9
The Journal of Organic Chemistry
Phenethyl 2-amino-2-oxoacetate (3e). White solid
chromatography on silica gel (PE/EtOAc = 3/1); mp: 73-
76 oC; 1H NMR (400 MHz, DMSO-d6) δ 8.15 (s, 1H), 7.89
(s, 1H), 4.30-4.22 (m, 2H), 1.07-0.98 (m, 2H), 0.04 (s,
9H). 13C NMR (100 MHz, DMSO-d6) δ 161.2, 159.1, 63.8,
16.6, -1.6. HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for
C7H15NO3SiNa 212.0713; Found 212.0710. IR (neat, cm-1):
υ 3368, 3244, 2958, 2902, 1682, 1230, 1207, 1176.
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(30.4 mg, 79% yield); purified by column chromatography
on silica gel (PE/EtOAc = 3/1); mp: 136-137 oC; 1H NMR
(400 MHz, DMSO-d6) δ 8.21 (s, 1H), 7.95 (s, 1H), 7.33-
7.21 (m, 5H), 4.38 (t, J = 6.9 Hz, 2H), 2.97 (t, J = 6.9 Hz,
2H). 13C NMR (100 MHz, DMSO-d6) δ 161.0, 158.8, 137.5,
128.9, 128.4, 126.5, 66.1, 34.0. HRMS (ESI-TOF) m/z: [M
+ Na]+ Calcd for C10H11NO3Na 216.0631; Found 216.0632.
IR (neat, cm-1): υ 3381, 3189, 2964, 1737, 1682, 1235, 971,
820.
3-methoxypropyl 2-amino-2-oxoacetate (3l). White
solid (25.7 mg, 80% yield); purified by column chroma-
tography on silica gel (PE/EtOAc = 2/1); mp: 76-79 oC; 1H
NMR (400 MHz, DMSO-d6) δ 8.20 (s, 1H), 7.93 (s, 1H),
4.20 (t, J = 6.4 Hz, 2H), 3.40 (t, J = 6.4 Hz, 2H), 3.23 (s,
3H), 1.91-1.84 (m, 2H). 13C NMR (100 MHz, DMSO-d6) δ
161.1, 158.9, 68.2, 63.0, 57.9, 28.1. HRMS (ESI-TOF) m/z:
[M + Na]+ Calcd for C6H11NO4Na 184.0580; Found
184.0587. IR (neat, cm-1): υ 3380, 3214, 2874, 2809, 1682,
1235, 1129, 1097.
9
Furan-2-ylmethyl 2-amino-2-oxoacetate (3f). Light
yellow solid (14.2 mg, 42% yield); purified by column
chromatography on silica gel (PE/EtOAc = 4/1); mp: 113-
115 oC; 1H NMR (400 MHz, DMSO-d6) δ 8.28 (s, 1H), 7.98
(s, 1H), 7.73 (d, J = 1.0 Hz, 1H), 6.61 (d, J = 3.1 Hz, 1H),
6.61-6.49 (m, 1H), 5.21 (s, 2H). 13C NMR (100 MHz,
DMSO-d6) δ 160.7, 158.6, 148.4, 144.1, 111.8, 110.9, 59.0.
HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for C7H7NO4Na
192.0267; Found 192.0276. IR (neat, cm-1): υ 3349, 3237,
2971, 1682, 1229, 1200, 1152, 931.
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Phenyl 2-amino-2-oxoacetate (3m). Yellow solid (13.9
mg, 42% yield); purified by column chromatography on
silica gel (PE/EtOAc = 3/1); mp: 130-131 oC; 1H NMR (400
MHz, DMSO-d6) δ 8.50 (s, 1H), 8.17 (s, 1H), 7.49-7.45 (m,
2H), 7.34-7.30 (m, 1H), 7.26-7.24 (m, 2H). 13C NMR (100
MHz, DMSO-d6) δ 159.5, 158.2, 150.1, 129.7, 126.4, 121.4.
HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for C8H7NO3Na
188.0318; Found 188.0323. IR (neat, cm-1): υ 3412, 3240,
2921, 2850, 1760, 1683, 1206, 1176.
Cinnamyl 2-amino-2-oxoacetate (3g). White solid
(23.6 mg, 58% yield); purified by column chromatography
on silica gel (PE/EtOAc = 3/1); mp: 143-145 oC; 1H NMR
(400 MHz, DMSO-d6) δ 8.28 (s, 1H), 7.99 (s, 1H), 7.50-
7.48 (m, 2H), 7.38-7.34 (m, 2H), 7.31-7.27 (m, 1H), 6.77
(d, J = 16.0 Hz, 1H), 6.45-6.38 (m, 1H), 4.86 (d, J = 5.6
Hz, 2H). 13C NMR (100 MHz, DMSO-d6) δ 160.8, 158.9,
135.8, 134.2, 128.7, 128.2, 126.6, 122.7, 66.0. HRMS (ESI-
TOF) m/z: [M + Na]+ Calcd for C11H11NO3Na 228.0631;
Found 228.0637. IR (neat, cm-1): υ 3398, 3214, 2921,
2850, 1681, 1252, 1207, 1180.
(3S,8S,9S,10R,13R,14S,17R)-10,13-dimethyl-17-((R)-6-
methylheptan-2-yl)-2,3,4,7,8,9,10,11,12,13,14,15,16,17-
tetradecahydro-1H-cyclopenta[a]phenanthren-3-yl
2-
amino-2-oxoacetate (3n). White solid (49.3 mg, 54%
yield); purified by column chromatography on silica gel
(PE/EtOAc = 2/1); mp: 234-236 oC; 1H NMR (400 MHz,
CDCl3) δ 6.99 (s, 1H), 6.22 (s, 1H), 5.42 -5.40 (m, 1H),
4.82-4.73 (m, 1H), 2.56-2.49 (m, 1H), 2.42-2.37 (m, 1H),
2.03-0.82 (m, 38H), 0.68 (s, 3H). 13C NMR (100 MHz,
CDCl3) δ 159.5, 158.7, 138.9, 123.4, 56.7, 56.1, 50.0, 42.3,
39.7, 39.5, 37.6, 36.8, 36.5, 36.2, 35.8, 31.9, 31.8, 28.2,
28.0, 27.3, 24.2, 23.8, 22.8, 22.5, 21.0, 19.2, 18.7, 11.8.
HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for C29H47NO3Na
480.3448; Found 480.3448. IR (neat, cm-1): υ 3403, 3218,
2935, 2867, 1735, 1698, 1400, 1215.
Ethyl 2-amino-2-oxoacetate (3h). White solid (15.0
mg, 65% yield); purified by column chromatography on
silica gel (PE/EtOAc = 2/1); mp: 114-116 oC; 1H NMR (400
MHz, DMSO-d6) δ 8.20 (s, 1H), 7.92 (s, 1H), 4.21 (q, J =
7.1 Hz, 2H), 1.26 (t, J = 7.1 Hz, 3H). 13C NMR (100 MHz,
DMSO-d6) δ 161.1, 159.1, 61.7, 13.8. HRMS (ESI-TOF)
m/z: [M + Na]+ Calcd for C4H7NO3Na 140.0318; Found
140.0316. IR (neat, cm-1): υ 3374, 3201, 2989, 2941, 1732,
1682, 1238, 686.
Cyclohexyl 2-amino-2-oxoacetate (3i). White solid
(23.3 mg, 69% yield); purified by column chromatography
on silica gel (PE/EtOAc = 3/1); mp: 131-133 oC; 1H NMR
(400 MHz, DMSO-d6) δ 8.16 (s, 1H), 7.90 (s, 1H), 4.79-
4.73 (m, 1H), 1.83-1.81 (m, 2H), 1.72-1.68 (m, 2H), 1.55-
1.16 (m, 6H). 13C NMR (100 MHz, DMSO-d6) δ 160.5,
159.3, 74.2, 30.8, 24.7, 23.1. HRMS (ESI-TOF) m/z: [M +
Na]+ Calcd for C8H13NO3Na 194.0788; Found 194.0790.
IR (neat, cm-1): υ 3388, 3227, 2945, 2927, 2860, 1735,
1692, 1226.
(3S,8R,9S,10S,13S,14S)-10,13-dimethyl-17-oxohexa-
decahydro-1H-cyclopenta[a]phenanthren-3-yl-2-
amino-2-oxoacetate (3o). White solid (49.4 mg, 69%
yield); purified by column chromatography on silica gel
o
1
(PE/EtOAc = 2/1); mp: 215-217 C; H NMR (400 MHz,
CDCl3) δ 7.08 (s, 1H), 6.73 (s, 1H), 4.90-4.82 (m, 1H),
2.48-2.41 (m, 1H), 2.18-1.21 (m, 18H). 1.07-0.94 (m, 2H),
0.88-0.86 (m, 6H), 0.76-0.70 (m, 1H). 13C NMR (100
MHz, DMSO-d6) δ 219.6, 160.4, 159.2, 75.0, 53.6, 50.6,
47.1, 43.9, 36.0, 35.3, 35.2, 34.4, 33.2, 31.3, 30.3, 27.9,
26.7, 21.3, 20.1, 13.4, 11.9. HRMS (ESI-TOF) m/z: [M +
Na]+ Calcd for C21H31NO4Na 384.2145; Found 384.2135.
IR (neat, cm-1): υ 3423, 3241, 2935, 2839, 1739, 1689,
1395, 1213.
But-3-en-1-yl 2-amino-2-oxoacetate (3j). White solid
(12.0 mg, 43% yield); purified by column chromatography
o
1
on silica gel (PE/EtOAc = 3/1); mp: 81-82 C; H NMR
(400 MHz, DMSO-d6) δ 8.19 (s, 1H), 7.93 (s, 1H), 5.86-
5.75 (m, 1H), 5.30-4.90 (m, 2H), 4.21 (t, J = 6.7 Hz, 2H),
2.41 (q, J = 6.7 Hz, 2H). 13C NMR (100 MHz, DMSO-d6)
δ 161.0, 158.9, 134.1, 117.5, 64.6, 32.2. HRMS (ESI-TOF)
m/z: [M + Na]+ Calcd for C6H9NO3Na 166.0475; Found
166.0478. IR (neat, cm-1): υ 3387, 3235, 2964, 1733, 1681,
1406, 1238, 687.
2-oxo-2-phenylacetamide (5a). Light yellow solid
(19.2 mg, 65% yield); purified by column chromatography
o
1
on silica gel (PE/EtOAc = 5/1); mp: 82-84 C; H NMR
(400 MHz, DMSO-d6) δ 8.33 (s, 1H), 7.99-7.97 (m, 3H),
7.74-7.71 (m, 1H), 7.61-7.57 (m, 2H). 13C NMR (100 MHz,
DMSO-d6) δ 190.8, 167.2, 134.5, 132.7, 129.6, 128.9.
HRMS (ESI-TOF) m/z: [M + MeOH + Na]+ Calcd for
2-(trimethylsilyl)ethyl 2-amino-2-oxoacetate (3k).
White solid (29.7 mg, 79% yield); purified by column
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