10.1002/adsc.202000716
Advanced Synthesis & Catalysis
23.9 Hz, 1H), 5.05 (d, J = 34.0 Hz, 1H), 4.83 – 4.69 (m, 1H),
4.66 – 4.53 (m, 1H), 4.49 – 4.35 (m, 1H), 4.27 – 4.06 (m,
Methyl N-((tert-butoxycarbonyl)-L-phenylalanyl)-S-(2-
methoxy-1-(3-methoxyphenyl)-2-oxoethyl)-L-cysteinate
1
2H), 3.70 (d, J = 12.2 Hz, 3H), 3.19 – 2.80 (m, 4H), 2.33 (s, (3aj). White colloid (88.1 mg, 31% yield, d:r = 1:1.1). H
3H), 1.39 (s, 9H), 1.24 (1.28-1.20, 3H). 13C NMR (100 MHz, NMR (400 MHz, Chloroform-d) δ 7.32 – 7.16 (m, 6H), 7.05
Chloroform-d) δ 171.4, 170.8 (d, J = 7.9 Hz, 1C), 170.5 (d, – 6.79 (m, 4H), 5.21 – 5.02 (m, 1H), 4.82 – 4.71 (m, 1H),
J = 8.6 Hz, 1C), 155.3, 138.2, 136.6 (d, J = 3.6 Hz, 1C), 4.70 – 4.56 (m, 1H), 4.43 (s, 1H), 3.85 – 3.64 (m, 9H), 3.20
129.5, 129.4, 128.6, 128.5, 128.4, 126.9, 80.1, 61.9 (d, J = – 2.79 (m, 4H), 1.45 – 1.31 (m, 9H). 13C NMR (100 MHz,
6.4 Hz, 1C), 55.6, 52.7 (d, J = 2.7 Hz, 1C), 52.3, 51.8 (d, J = Chloroform-d) δ 171.4 (d, J = 9.8 Hz, 1C), 171.1 (d, J = 6.2
5.8 Hz, 1C), 38.4, 33.6 (d, J = 7.1 Hz, 1C), 28.3, 21.1, 14.1. Hz, 1C), 170.5 (d, J = 7.5 Hz, 1C), 159.8 (d, J = 2.3 Hz, 1C),
HRMS (ESI) m/z: calcd for C29H38N2O7SNa [M+Na]+: 155.4, 136.9 (d, J = 14.5 Hz, 1C), 136.5 (d, J = 4.5 Hz, 1C),
581.2292, found: 581.2280.
129.8, 129.3(8), 129.3(7), 128.6, 126.9, 120.9 (d, J = 0.98
Hz, 1C), 114.1(2), 114.0(7) (d, J = 3.1 Hz, 1C), 113.9, 80.2,
55.6, 55.3, 53.0 (d, J = 8.0 Hz, 1C), 52.7 (d, J = 4.9 Hz, 1C),
52.5, 52.0, 51.7 (d, J = 12.9 Hz, 1C), 38.3, 33.7 (d, J = 7.9
Hz, 1C), 28.2. HRMS (ESI) m/z: calcd for C28H30N2O8SNa
[M+Na]+: 583.2085, found: 583.2070.
Methyl N-((tert-butoxycarbonyl)-L-phenylalanyl)-S-(2-
ethoxy-2-oxo-1-(o-tolyl)ethyl)-L-cysteinate (3ag). White
colloid (182.8 mg, 65% yield, d:r = 1:0.9). H NMR (400
MHz, Chloroform-d) δ 7.42 (d, J = 7.6 Hz, 1H), 7.31 – 7.16
(m, 9H), 6.88 (d, J = 14.0 Hz, 1H), 5.03 (s, 1H), 4.91 – 4.82
(m, 1H), 4.79 – 4.71 (m, 1H), 4.24 – 4.15 (m, 2H), 3.71 (d, J
1
Methyl N-((tert-butoxycarbonyl)-L-phenylalanyl)-S-(2-
= 6.5 Hz, 3H), 3.17 – 2.87 (m, 4H), 2.41 (d, J = 4.5 Hz, 3H), ethoxy-1-(2-fluorophenyl)-2-oxoethyl)-L-cysteinate (3ak).
1
1.39 (s, 9H), 1.26 – 1.21 (m, 3H). 13C NMR (100 MHz, White colloid (159.3 mg, 57% yield, d:r = 1:2). H NMR
Chloroform-d) δ 171.2, 171.1 (d, J = 14.6 Hz, 1C), 170.5, (400 MHz, Chloroform-d) δ 7.57 – 7.46 (m, 1H), 7.33 –
155.3, 136.5, 136.4 (d, J = 14.0 Hz, 1C), 133.7 (d, J = 20.2 7.14 (m, 7H), 7.11 – 7.02 (m, 1H), 6.85 (d, J = 27.1 Hz, 1H),
Hz, 1C), 130.8 (d, J = 8.3 Hz, 1C), 129.4, 128.65, 128.62, 5.11 – 4.88 (d, J = 7.6 Hz, 2H), 4.77 (s, 1H), 4.40 (s, 1H),
128.32, 128.30, 128.2 (d, J = 8.3 Hz, 1C), 126.9, 126.5 (d, J 4.26 – 4.10 (m, 2H), 3.72 (d, J = 8.9 Hz, 3H), 3.18 – 2.90 (m,
= 2.2 Hz, 1C), 80.1, 62.1 (d, J = 2.0 Hz, 1C), 55.6, 52.7 (d, J 4H), 1.38 (d, J = 9.7 Hz, 9H), 1.28-1.20 (m, 3H). 13C NMR
= 3.0 Hz, 1C), 51.8 (d, J = 8.7 Hz, 1C), 49.1 (d, J = 27.3 Hz, (100 MHz, Chloroform-d) δ 171.2 (d, J = 7.0 Hz, 1C), 170.3
1C), 38.4, 33.8 (d, J = 36.1 Hz, 1C), 28.3, 19.5 (d, J = 0.9 (d, J = 4.1 Hz, 1C) 170.1, 161.2, 158.8, 155.3, 136.5 (d, J =
Hz, 1C), 14.1. HRMS (ESI) m/z: calcd for C29H38N2O7SNa 2.6 Hz, 1C), 130.1 (d, J = 3.3 Hz, 1C), 129.8 (d, J = 2.5 Hz,
[M+Na]+: 581.2292, found: 581.2276.
1C), 129.4 (d, J = 1.8 Hz, 1C), 128.7, 126.9, 124.6, 123.2(t,
J = 13.9 Hz, 1C), 115.7 (d, J = 4.4 Hz, 1C), 115.5 (d, J = 4.5
Hz, 1C), 80.2, 62.2 (d, J = 4.7 Hz, 1C), 55.6, 52.7 (d, J = 2.0
Hz, 1C), 51.9 (d, J = 6.5 Hz, 1C), 44.9 (d, J = 23.6 Hz, 1C),
38.3, 34.0 (d, J = 33. 9 Hz, 1C), 28.2, 14.0. 19F NMR (376
MHz, Chloroform-d) δ 117.06, 117.13. HRMS (ESI) m/z:
calcd for C28H35FN2O7SNa [M+Na]+: 585.2041, found:
585.2030.
Methyl N-((tert-butoxycarbonyl)-L-phenylalanyl)-S-(2-
ethoxy-1-(4-methoxyphenyl)-2-oxoethyl)-L-cysteinate
(3ah). White colloid (218.2 mg, 76% yield, d:r = 1:1). H
1
NMR (400 MHz, Chloroform-d) δ 7.42 – 7.28 (m, 3H), 7.25
– 7.16 (m, 4H), 6.92 – 6.80 (m, 3H), 5.17 – 4.96 (m, 1H),
4.82 – 4.70 (m, 1H), 4.67 – 4.53 (m, 1H), 4.42 (s, 1H), 4.24
– 4.12 (m, 2H), 3.79 (d, J = 2.3 Hz, 3H), 3.71 (d, J = 11.4
Hz, 3H), 3.15-2.81 (m, 4H), 1.39 (d, J = 2.9 Hz, 9H), 1.27 –
Methyl N-((tert-butoxycarbonyl)-L-phenylalanyl)-S-(2-
1.22 m, 3H). 13C NMR (100 MHz, Chloroform-d) δ 171.4, ethoxy-1-(naphthalen-1-yl)-2-oxoethyl)-L-cysteinate (3al).
1
170.9 (d, J = 10.1 Hz, 1C), 170.5 (d, J = 9.0 Hz, 1C), 159.6, White colloid (214.2 mg, 72% yield, d:r = 1:0.9). H NMR
155.3, 136.5 (d, J = 4.2 Hz, 1C), 129.8, 129.7, 129.4, 128.6, (400 MHz, Chloroform-d) δ 8.14 (t, J = 9.2 Hz, 1H), 7.90 –
126.9, 114.1, 80.1, 61.9 (d, J = 6.7 Hz, 1C), 55.3, 52.7 (d, J 7.78 (m, 2H), 7.65 – 7.43 (m, 4H), 7.28 – 7.14 (m, 5H), 7.05
= 2.3 Hz, 1C), 51.9, 51.6, 51.4, 38.3, 33.6 (d, J = 12.3 Hz, (d, J = 24.7 Hz, 1H), 5.41 (d, J = 19.0 Hz, 1H), 5.15 – 4.96
1C), 28.2, 14.1. HRMS (ESI) m/z: calcd for C29H38N2O8SNa (m, 1H), 4.87-4.70 (m, 1H), 4.42 (s, 1H), 4.26 – 4.07 (m,
[M+Na]+: 597.2241, found: 597.2225.
2H), 3.61 (d, J = 9.3 Hz, 3H), 3.19 – 2.83(m, 4H), 1.37 (d, J
= 5.8 Hz, 9H), 1.24 – 1.10 (m, 3H). 13C NMR (100 MHz,
Chloroform-d) δ 171.4, 171.2, 170.6, 155.3, 136.6, 134.1,
130.9, 129.4, 129.3, 129.0 (d, J = 3.9 Hz, 1C), 128.6 (d, J =
3.9 Hz, 1C), 126.9, 126.8, 126.7, 126.1 (d, J = 5.2 Hz, 1C),
125.3, 123.4, 123.3, 80.1, 62.2, 55.6, 52.7, 51.7 (d, J = 12.2
Hz, 1C), 49.8, 49.2, 38.4, 34.0 (d, J = 41.3 Hz, 1C), 28.27,
14.0. HRMS (ESI) m/z: calcd for C32H38N2O7SNa [M+Na]+:
617.2292, found: 617.2275.
Methyl N-((tert-butoxycarbonyl)-L-phenylalanyl)-S-(2-
methoxy-1-(4-methoxyphenyl)-2-oxoethyl)-L-cysteinate
(3ai). White colloid (224.0 mg, 80% yield, d:r = 1:1). H
NMR (400 MHz, Chloroform-d) δ 7.38 – 7.17 (m, 7H), 6.98
– 6.80 (m, 3H), 5.21 – 5.06 (m, 1H), 4.83 – 4.70 (m, 1H),
4.70 – 4.57 (m, 1H), 4.42 (s, 1H), 3.78 (d, J = 2.4 Hz, 3H),
3.74 – 3.63 (m, 6H), 3.20 – 2.77 (m, 4H), 1.39 (d, J = 3.2 Hz,
9H). 13C NMR (100 MHz, Chloroform-d) δ 171.4, 171.3,
170.5 (d, J = 10.0 Hz, 1C), 159.6, 155.3, 136.5 (d, J = 4.5
1
Methyl N-((tert-butoxycarbonyl)-L-alanyl)-S-(2-ethoxy-
Hz, 1C), 129.8, 129.7, 129.4, 128.6, 126.9, 114.2, 80.1, 55.3, 1-(4-methoxyphenyl)-2-oxoethyl)-L-cysteinate
(3am).
52.8 (d, J = 8.1 Hz, 1C), 52.7 (d, J = 4.3 Hz, 1C), 51.8, 51.7, White colloid (batch: 176.8 mg, 71% yield, flow: 190.3 mg,
1
51.3, 38.3, 33.7, 33.6, 28.2. HRMS (ESI) m/z: calcd for 76% yield, d:r = 1:0.9). H NMR (400 MHz, Chloroform-d)
C28H36N2O8SNa [M+Na]+: 583.2085, found: 583.2070.
δ 7.36 (t, J = 8.7 Hz, 2H), 7.06 – 6.92 (m, 1H), 6.87 (d, J =
This article is protected by copyright. All rights reserved.