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A. S. Saghyan et al. · Enantiomerically Enriched α-Amino Acids
7.12 (1H, ddd, J1 = 8.7, J2 = 6.8, J3 = 1.8, H-5 C6H4); 7.17 Complex 11a
(1H, m, H-4 Ph); 7.21 – 7.37 (4H, m, H arom.); 7.43 – 7.56
Yield 60%. M. p. 230 – 232 ◦C. – [α]D20 = +840.0◦ (c =
(2H, m, H arom.); 7.99 (2H, m, H-2,6 Ph); 8.24 (1H, dd,
J1 = 8.7, J2 = 1.1, H-6 C6H4); 7.31 (1H, dd, J1 = 1.9,
J2 = 0.8, H-5 furan). – 13C NMR (CDCl3-CCl4 ∼ 1 : 1):
δ = 22.4 and 22.5 (CH3), 23.9 (γ-C proline), 26.1 (CH i-Bu),
30.8 (β-C proline), 34.0 (CH2 i-Bu), 41.0 (CH2-furan); 51.6
(CH2CH), 57.3 (δ-C proline), 62.9 (CH2Ph), 68.0 (CHCH2),
70.4 (α-C proline), 110.1 (C-3 furan); 111.1 (C-4 furan),
120.2 (C-4 C6H4), 123.8 (C-6 C6H4), 126.2 (C*), 127.5
(CH), 128.0 (CH), 127.7 (CH), 128.8 (C-2.6 P?), 128.8 (CH),
129.0 (CH), 129.7 (CH), 131.6 (C-3.5 PH), 132.2 (C-5 fu-
ran), 133.4 (C-5 C6H4), 133.5 (C*), 142.2 (C*), 143.2 (C*),
148.0 (C*), 150.1 (C*), 168.4 (C*), 171.6 (C*), 175.4 (C*),
180.0 (C*):
0.05; MeOH). – Analysis: found (%) C 61.67, H 4.66, N
11.92; calcd. for C37H34N6NiO4S (%) C 61.95, H 4.74, N
11.72. – 1H NMR (CDCl3-CCl4 = 1 : 1): δ = 1.98 (1H, m,
γ-Ha pro), 2.04 (1H, m, δ-Ha pro), 2.46 (1H, m, β-Ha pro),
2.77(1H, m, β-Hb pro), 3.40 (1H, dd, J1 = 10.6, J2 = 6.2,
α-H pro), 3.40 (1H, m, dd,J1 = 10.6, J2 = 6.2, α-H pro),
3.48 (1H, m, γ−Hb pro), 3.53 (1H, m, δ-Hb Pro), 3.56 (1H,
d,J = 12.6, CH2C6H5), 4.38 (1H, d, J = 12.6, CH2C6H5),
4.49 (1H, t, J = 6.2, CH), 4.84(1H, dd, J1 = 13.7, J2 = 6.2,
CH2CH), 4.91 (1H, dd, J1 = 13.7, J2 = 6.2, CH2CH), 4.93
(2H, dt, J1 = 5.5, J2 = 1.3, CH2All), 5.20 (1H, m, = CH2),
5.21 (1H, m, = CH2), 5.90 (1H, ddt, J1 = 17.2, J2 = 10.2,
J3 = 5.5, = CH), 6.55 (1H, dd, J1 = 3.5, J2 = 1.8, H-4 furan),
6.60 (1H, dd, J1 = 8.3, J2 = 2.2, H-3 C6H4), 6.64 (1H, ddd,
J1 = 8.3, J2 = 6.4, J3 = 1.1, H-4 C6H4), 6.87(1H, d, J = 3.5,
H-5 furan), 7.09 – 7.22 (3H, m, Ar), 7.27 – 7.37 (4H, m, Ar),
7.44 (1H, tt, J1 = 7.5, J2 = 1.3, H-4 C6H5), 7.53(1H, td,
J1 = 7.6, J2 = 1.4, Ar.), 7.58 (1H, d, J = 1.8, H-3 furan), 8.02
(2H, m, H-2,6 C6H5), 8.27(1H, dd, J1 = 8.7, J2 = 1.1, H-6
C6H4). – 13C NMR (CDCl3-CCl4 ∼ 1 : 1): δ = 24.1 (γ-C
pro), 31.0 (β-C pro), 48.2 (CH2 all), 52.1 (CH2CH), 57.5(δ-
C pro), 63.3 (CH2 Ph), 68.4(CH), 70.7 (α-C pro), 112.2
(C-4 furan), 113.4 (C-5 furan), 119.1 (=CH2), 120.7 (C-4
C6H4), 123.9(C-6 C6H4), 126.6 (CH), 128.4 (CH), 129.0 (C-
3,5 C6H5 CH2), 129.1 (CH), 129.1 (CH), 129.2 (CH), 129.9
(CH), 130.6 (=CH), 131.8 (C-2,6 C6H5CH2), 132.7 (CH),
133.4 (C-3 C6H4), 133.8 (C), 133.9 (C), 140.9 (C), 143.4
(C), 144.6 (C-3 furan), 169.5 (C), 172.6 (C), 176.1 (C), 180.3
(C).
Complex 10b
Yield 69%. M. p. 147 – 148 ◦C. – [α]D20 = +1943.2◦ (c =
0.25, CH3OH). – Analysis: found (%) C 59.92, H 4,85, N
10,81; calcd. for C39H39N6O4SNi (%) C 59.90, H 4.99, N
10.75. – 1H NMR (CDCl3): δ = 0.94 (3H, d, J = 6.6, CH3),
0.95 (3H, d, J = 6.6, CH3), 1.96 (1H, m, CH i-Bu), 2.06
(1H, m, δ-Ha proline), 2.18 (1H, m, γ-Ha pro), 2.45 (1H,
dd, J1 = 15.6, J2 = 6.9, CH2i-Bu), 2.50 (1H, dd, J1 = 15.6,
J2 = 7.1, CH2i-Bu), 2.58 (1H, m, β-Ha pro), 3.02 (1H, m, β-
Hb pro), 3.47 (1H, dd, J1 = 10.8, J2 = 6.6, α-H proline),
3.52 (1H, m, δ-Hb Proline), 3.74 (1H, m, γ-Hb proline),
3.87 (1H, d, J = 12.9, CH2C6H4Cl), 4.38 (1H, dd, J1 = 7.0,
J2 = 6.8, CHCH2N), 4.44 (1H, d, J = 12.9, CH2C6H4Cl),
4.76 (1H, dd, J1 = 13.5, J2 = 6.8, CH2CH), 4.83 (1H, dd,
J1 = 13.5, J2 = 7.0, CH2CH), 5.06 (1H, d, J = 15.7,CH2-
furan), 5.22 (1H, d, J = 15.7, CH2-furan), 6.28 (1H, dd, J1 =
3.3, J2 = 1.9, H-4 furan), 6.57 (1H, dd, J1 = 8.2, J2 = 1.8,
H-3 C6H4), 6.63 (1H, dd, J1 = 8.2, J2 = 6.8, J3 = 1.1, H-
Complex 11b
Yield 62%. M. p. 234 – 236 ◦C. – [α]D20 = +876.0◦ (c =
4 C6H4), 6.80 (1H, d. br., J = 7.7, H-2 C6H5), 7.12 (1H, 0.05; MeOH). – Analysis: found (%) C 59.30, H 4.30, N
ddd, J1 = 8.7, J2 = 6.8, J3 = 1.8, H-5 C6H4), 7.16 (1H, 11.12; calcd. for C37H33ClN6NiO4S (%) C 59.11, H 4.39,
1
ddd,J1 = 7.7, J2 = 7.7, J3 = 1.8, C6H4Cl), 7.22 – 7.35 (5H, N 11.18. – H NMR (CDCl3-CCl4 = 1 : 1): δ = 2.06 (1H,
m, H-5 furan, H-3,4,5,6 C6H5), 7.47 (1H, ddd, J1 = 8.8, J2 = m, δ-H pro), 2.06 (1H, m, γ-H pro), 2.56 (1H, m, β-H pro),
7.6, J3 = 1.4, C6H4Cl), 7.54 (1H, ddd, J1 = 7.6, J2 = 37.4, 2.97 (1H, m, β-H pro), 3.48 (1H, dd, J1 = 10.5, J2 = 6.6, α-
J3 = 1.4, C6H4Cl), 8.16 (1H, dd, J1 = 8.7, J2 = 1.1, H-6 H pro), 3.48 (1H, m, γ-H pro), 3.57 (1H, m, δ-H pro), 3.85
C6H4), 8.26 (1H, dd, J1 = 7.6, J2 = 1.6, H-3 C6H4Cl). – 13
C
(1H, d, J = 12.9, CH2-Ar), 4.40 (1H, d, J = 12.9, CH2-Ar),
NMR (CDCl3-CCl4 ∼ 1 : 1): δ = 22.7 (CH3), 24.0 (γ-C pro- 4.48 (1H, t, J = 6.2, CH), 4.84 (2H, d, J = 6.2, CHCH2N),
line), 26.3 (CH i-Bu), 30.8 (β-C proline), 34.3 (CH2i-Bu), 4.93 (2H, dt, J1 = 5.5, J2 = 1.4, NCH2 Allyl), 5.20 (1H,
41.2 (CH2 furan), 51.8 (CH2CH), 57.6 (δ-C proline), 59.7 m, = CH2), 5.21 (1H, m, = CH2), 5.90 (1H, ddt, J1 = 17.1,
(CH2C6H4Cl), 68.3 (CHCH2), 71.1 (α-C proline), 110.4 (C- J2 = 10.3, J3 = 5.5, = CH), 6.56 (1H, dd, J1 = 3.5, J2 = 1.8,
3 furan), 111.4 (C-4 furan), 120.5 (C-4 C6H4), 124.0 (C-6 H-4 furan), 6.62 (1H, dd, J1 = 8.3, J2 = 2.4, H-3 C6H4),
C6H4), 126.7 (C*), 127.2 (CH), 127.8 (CH), 128.3 (CH), 6.66 (1H, ddd, J1 = 8.3, J2 = 6.3, J3 = 1.0, H-4 C6H4),
129.0 (CH), 129.2 (CH), 129.8 (CH), 130.5 (CH), 130.5 6.87 (1H,dd, J1 = 3.5, J2 = 0.8, H-5 furan ), 7.09 – 7.19
(CH), 131.5 (C*), 132.5 (C-5 furan), 133.7 (C-5 C6H4), (3H, m, Ar), 7.25 – 7.36 (4H, m, Ar), 7.44 (1H, tt, J1 = 7.5,
133.8 (CH), 134.4 (C-3 C6H4Cl), 136 (C*), 142.3 (C*), J2 = 1.3, Ar), 7.54 (1H, td, J1 = 7.5, J2 = 1.3, Ar), 7.58 (1H,
143.4 (C*), 148.2 (C*), 150.2 (C*), 168.7 (C*), 171.9 (C*), dd, J1 = 1.8, J2 = 0.8, H-3 furan), 8.17 (1H, dd, J1 = 8.7,
175.5 (C*), 179.2 (C*).
J2 = 1.0, C6H4 ), 8.23 (1H, dd, J1 = 7.6, J2 = 1.6, C6H4Cl).
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