10.1002/asia.202001003
Chemistry - An Asian Journal
FULL PAPER
= 10.5, 3.5 Hz, 1H), 3.88-3.67 (m, 3H), 3.59-3.45 (m, 2H), 2.49-2.41 (m,
2H), 2.26-2.20 (m, 1H), 2.01-1.96 (m, 4H), 1.43-1.41 (m, 3H), 1.38-1.36
(m, 3H), 1.24 (q, J = 14.7, 7.3 Hz, 6H); 13C NMR (150 MHz, D2O) δ 175.7,
175.4, 175.04, 175.02, 174.9, 174.2, 173.9, 172.9, 94.9, 90.9, 82.5, 79.5,
78.0, 77.7, 75.7, 71.4, 68.9, 68.7, 62.7, 61.8, 60.6, 60.4, 56.1, 53.7, 51.9,
49.6, 49.5, 46.1, 46.0, 30.1, 25.94, 25.90, 25.6, 22.2, 21.9, 18.6, 16.7,
13.3, 13.2; HRMS (ESI-TOF) m/z calcd for C23H39N3O12 + Na+: 572.2426
[M+Na]+; found: 572.2428.
173.9, 173.2, 94.9, 90.9, 82.4, 79.4, 78.0, 77.7, 75.7, 71.4, 68.9, 68.7,
66.3, 60.6, 60.4, 56.1, 53.7, 52.3, 49.54, 49.50, 30.8, 29.7, 25.94, 25.91,
22.2, 22.0, 21.9, 18.6, 18.4, 16.77, 16.76, 12.8; HRMS (ESI-TOF) m/z
calcd for C23H39N3O12 + Na+: 572.2426 [M+Na]+; found: 572.2425.
Compound 25. The reaction was carried out as described above in 18.
The final product, 25 (20 mg, 14% over 3 steps) was obtained from S9;
1H NMR (600 MHz, D2O) (Anomers-1.00α : 0.47β) δ 5.16 (d, J = 3.5 Hz,
0.64H), 4.66 (d, J = 8.5 Hz, 0.30H), 4.46 – 4.42 (m, 3H), 4.32 – 4.22 (m,
2H), 3.95 – 3.48 (m, 8H), 2.36 – 2.33 (m, 2H), 2.21 – 2.19 (m, 1H), 2.02 –
Compound 20. Lithium hydroxide (2.0 N) was added to the solution of
19 in THF. After stirring for 1 h, the mixture was neutralized with Dowex,
filtered, and concentrated. The crude product was purified by cc to afford
20 (29 mg, 34%) as a white solid; 1H NMR (600 MHz, D2O) (Anomers-
1.00α : 0.60β) δ 5.14 (d, J = 3.5 Hz, 1H), 4.31-4.19 (m, 3H), 3.94 (dd, J =
10.5, 3.5 Hz, 1H), 3.92-3.68 (m, 3H), 3.58-3.45 (m, 2H), 2.30-2.23 (m,
2H), 2.13-2.05 (m, 1H), 1.95 (s, 3H), 1.91-1.85 (m, 1H), 1.43-1.41 (m,
3H), 1.38-1.36 (m, 3H). 13C NMR (150 MHz, D2O) δ 179.8, 177.9, 175.7,
174.2, 174.0, 94.9, 90.9, 82.3, 79.5, 78.0, 77.8, 75.6, 71.5, 69.0, 60.4,
56.0, 54.4, 53.6, 49.6, 32.1, 27.8, 21.9, 18.6, 16.9; HRMS (ESI-TOF) m/z
calcd for C19H31N3O12 + Na+: 516.1800 [M+Na]+; found: 516.1803.
1.97 (m, 4H), 1.43 (dd, J = 7.3, 4.4 Hz, 3H), 1.37 (t, J = 6.1 Hz, 3H); 13
C
NMR (150 MHz, D2O) δ 179.62, 179.58, 175.7, 175.4, 175.0, 174.2,
174.0, 172.7, 94.9, 90.8, 82.4, 79.4, 78.0, 77.7, 75.7, 71.5, 69.0, 68.7,
65.6, 60.4, 56.1, 53.7, 52.49, 52.47, 49.54, 49.50, 41.8, 32.1, 26.5, 26.4,
22.2, 21.9, 18.6, 16.8, 16.5;
HRMS (ESI-TOF) m/z calcd for
C21H34ClN3O12 + H+: 556.1904 [M+H]+; found: 556.1905.
Compound 26. The reaction was carried out as described above in 18.
The final product, 26 (40 mg, 35% over 3 steps) was obtained from S7;
1H NMR (600 MHz, D2O) (Anomers-1.00α : 0.48β) δ 5.16 (d, J = 3.5 Hz,
0.63H), 4.66 (d, J = 8.5 Hz, 0.30H), 4.35 – 4.22 (m, 3H), 3.95 – 3.49 (m,
6H), 2.38 – 2.28 (m, 2H), 2.21 – 2.10 (m, 1H), 2.06 – 1.92 (m, 4H), 1.85 –
1.75 (m, 2H), 1.74 – 1.61 (m, 2H), 1.53 – 1.45 (m, 3H), 1.42 (dd, J = 7.2,
4.1 Hz, 3H), 1.40 – 1.24 (m, 6H). 13C NMR (150 MHz, D2O) δ 179.5,
179.4, 175.6, 175.3, 174.9, 174.2, 173.9, 172.8, 94.9, 90.8, 82.3, 79.3,
78.0, 77.6, 75.7, 75.3, 71.5, 69.0, 68.7, 60.6, 60.4, 56.1, 53.7, 53.0,
52.89, 52.87, 49.5, 49.4, 49.0, 32.4, 31.9, 30.69, 30.65, 30.61, 26.6, 26.4,
26.3, 24.7, 22.9, 22.8, 22.2, 21.9, 18.59, 18.57, 16.8, 16.5; HRMS (ESI-
TOF) m/z calcd for C25H41N3O12 + H+: 576.2763 [M+H]+; found: 576.2761.
Compound 21. The reaction was carried out as described above in 18.
The final product, 21 (58 mg, 40% over 3 steps) was obtained from S14;
1H NMR (600 MHz, CD3OD) (Anomers-1.00α : 0.20β) δ 5.16 (d, J = 3.4
Hz, 1H), 4.39-4.33 (m, 2H), 4.29-4.26 (m, 1H), 4.13 (q, J = 7.1 Hz, 2H)
3.87 (dd, J = 10.4, 3.2 Hz, 1H), 3.82-3.78 (m, 2H), 3.72 (dd, J = 11.9, 5.2
Hz, 1H), 3.63 (dd, J = 10.4, 8.9 Hz, 1H), 3.49 (t, J = 9.5 Hz, 1H), 2.43-
2.40 (m, 2H), 2.25-2.10 (m, 1H), 1.95-1.88 (m, 4H), 1.40-1.38 (m, 6H),
1.25 (t, J = 7.1 Hz, 3H); 13C NMR (150 MHz, CD3OD) δ 175.2, 174.9,
174.0, 173.0, 172.1, 91.0, 79.0, 76.7, 71.8, 70.2, 60.3, 54.1, 52.3, 49.4,
30.1, 26.5, 21.5, 18.3, 16.3, 13.1; HRMS (ESI-TOF) m/z calcd for
C21H36N4O11 + Na+: 543.2273 [M+Na]+; found: 543.2289.
Compound 27. The reaction was carried out as described above in 18.
The final product, 27 (32 mg, 21% over 3 steps) was obtained from S8.
1H NMR (600 MHz, D2O) (Anomers-1.00α : 0.51β) 7.36 – 7.23 (m, 5H), δ
5.15 (d, J = 3.5 Hz, 0.63H), 4.64 (d, J = 8.4 Hz, 0.32H), 4.43 – 4.37 (m,
1H), 4.38 – 4.32 (m, 2H), 4.31 – 4.18 (m, 2H), 3.98 – 3.41 (m, 6H), 2.94
(t, J = 6.4 Hz, 2H), 2.25 (t, J = 7.4 Hz, 2H), 2.06 – 1.97 (m, 1H), 1.93 (d, J
= 4.7 Hz, 3H), 1.88 – 1.74 (m, 1H), 1.36 (dd, J = 6.2, 5.6 Hz, 6H); 13C
NMR (150 MHz, D2O) δ 176.91, 176.88, 175.5, 175.3, 174.6, 174.2,
173.9, 172.6, 138.1, 129.0, 128.6, 126.7, 94.9, 90.9, 82.3, 79.4, 78.0,
77.6, 75.7, 71.4, 69.0, 68.7, 66.4, 60.6, 60.5, 56.1, 53.6, 51.9, 49.43,
49.39, 34.1, 29.9, 25.7, 22.2, 21.9, 18.6, 16.8. HRMS (ESI-TOF) m/z
calcd for C27H39N3O12 + H+: 598.2607 [M+H]+; found: 598.2617.
Compound 22. The reaction was carried out as described above in 18.
The final product, 22 (94 mg. 31% over 3 steps) was obtained from S15;
1H NMR (600 MHz, D2O) (Anomers-1.00α : 0.50β) δ 5.18 (d, J = 3.5 Hz,
1H), 4.34-4.19 (m, 4H), 3.98 (dd, J = 10.5, 3.5 Hz, 1H), 3.90-3.71 (m, 4H),
3.62-3.50 (m, 2H), 2.35-2.32 (m, 2H), 2.16-2.06 (m, 1H), 2.00-1.94 (m,
4H), 1.46-1.39 (m, 6H); 13C NMR (150 MHz, D2O) δ 178.6, 177.7, 175.8,
175.6, 174.2, 174.1, 173.99., 173.96, 94.9, 90.9, 82.5, 79.6, 79.5, 78.1,
77.8, 75.7, 71.5, 69.0, 68.8, 60.7, 60.5, 56.1, 54.5, 54.3, 53.7, 49.6, 49.5,
31.52, 31.50, 27.8, 22.2, 22.0, 18.7, 18.6, 16.8, 16.5; HRMS (ESI-TOF)
m/z calcd for C19H32N4O11 + Na+: 515.1960 [M+Na]+; found: 515.1944.
Compound 23. The reaction was carried out as described above in
18.The final product, 23 (76 mg, 48% over 3 steps) was obtained from
S17; 1H NMR (600 MHz, D2O) (Anomers-1.00α : 0.50β) δ 5.15 (d, J = 3.4
Hz, 1H), 4.55 (t, J = 12.7, 6.4 Hz, 1H), 4.30-4.23 (m, 2H), 3.97 (dd, J =
10.4, 3.4Hz, 1H), 3.91-3.69 (m, 4H), 3.59-3.49 (m, 2H), 2.66 (d, J = 6.4
Hz, 2H), 1.98 (s, 3H), 1.43-1.38 (m, 6H); 13C NMR (150 MHz, D2O) δ
177.7, 176.2, 175.9, 174.61, 174.60, 174.2, 173.9, 94.8, 90.94, 90.92,
82.4, 79.6, 78.01, 78.0, 77.72, 77.71, 75.6, 71.4, 68.8, 68.7, 60.6, 60.5,
56.1, 53.7, 51.0, 49.70, 49.69, 38.3, 22.2, 22.0, 18.7, 18.4; HRMS (ESI-
TOF) m/z calcd for C18H30N4O11 + Na+: 501.1803 [M+Na]+; found:
501.1792.
Compound 28. The reaction was carried out as described above in 18.
The final product, 28 (50 mg, 40% over 3 steps) was obtained from S10;
1H NMR (600 MHz, D2O) (Anomers-1.00α : 0.42β) δ 5.14 (d, J = 3.5 Hz,
0.64H), 4.66 (d, J = 8.5 Hz, 0.27H), 4.32 – 4.07 (m, 3H), 4.00 – 3.44 (m,
6H), 3.25 – 3.12 (m, 2H), 2.48 – 2.40 (m, 2H), 2.18 – 2.09 (m, 1H), 2.00 –
1.89 (m, 4H), 1.49 – 1.43 (m, 2H), 1.41 (dd, J = 7.2, 4.1 Hz, 3H), 1.37 (dd,
J = 6.8, 4.4 Hz, 3H), 1.31 – 1.23 (m, 2H), 0.86 (t, J = 7.4 Hz, 3H); 13C
NMR (150 MHz, D2O) δ 178.8, 175.8, 175.6, 175.0, 174.9, 174.2, 173.9,
173.1, 173.0, 94.9, 90.9, 82.5, 79.6, 78.1, 77.7, 75.7, 71.4, 68.9, 68.6,
60.6, 60.4, 56.1, 54.3, 53.7, 53.6, 53.55, 53.51, 49.7, 42.5, 39.2, 39.1,
31.5, 30.4, 26.8, 26.78, 22.1, 21.9, 19.33, 19.28, 18.6, 17.7, 16.6, 16.2,
12.9, 12.1; HRMS (ESI-TOF) m/z calcd for C23H40N4O11 + H+: 549.2766
[M+H]+; found: 549.2770.
Compound 24. The reaction was carried out as described above in 18.
The final product, 24 (20 mg, 13% over 3 steps) was obtained from S2;
1H NMR (600 MHz, D2O) (Anomers-1.00α : 0.50β) δ 5.16 (d, J = 3.5 Hz,
0.6H), 4.66 (d, J = 8.5 Hz, 0.3H), 4.41 (dd, J = 9.2, 5.3 Hz, 1H), 4.33 –
4.20 (m, 2H), 4.16 (t, J = 6.5 Hz, 2H), 3.98 – 3.44 (m, 6H), 2.43 – 2.37 (m,
2H), 2.23 – 2.15 (m, 1H), 2.05 – 1.93 (m, 4H), 1.66 – 1.59 (m, 2H), 1.42
Compound 29. The reaction was carried out as described above in 18.
The final product, 29 (45 mg, 34% over 3 steps) was obtained from S11;
1H NMR (600 MHz, D2O) (Anomers-1.00α : 0.50β) δ 5.15 (d, J = 3.5 Hz,
0.62H), 4.67 (d, J = 8.5 Hz, 0.31H), 4.32 – 4.07 (m, 3H), 4.01 – 3.44 (m,
6H), 3.25 – 3.11 (m, 2H), 2.41 – 2.30 (m, 2H), 2.16 – 2.05 (m, 1H), 2.00 –
(dd, J = 7.3, 4.3 Hz, 3H), 1.39 – 1.31 (m, 5H), 0.89 (t, J = 7.4 Hz, 3H); 13
NMR (150 MHz, D2O) δ 178.03, 177.99, 175.7, 175.4, 174.9, 174.2,
C
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