J
C. Bier et al.
Feature
Synthesis
3.63 (m, 1 H, 3-H), 3.51 (mc, 6a/b-H), 3.44 (ddd, 3J2,3 = 9.6 Hz, 3J2,1 = 7.7
Hz, 3J2,2-OH = 4.9 Hz, 1 H, 2-H), 3.41–3.35 (m, 1 H, 5-H), 3.34–3.28 (m, 1
H, 4-H).
13C NMR (151 MHz, DMSO-d6): δ = 152.54 (C-7a), 146.56 (C-3a),
140.19 (C-6′), 133.16 (C-5′), 107.24 (C-4′), 105.00 (C-7′), 103.37 (C-2′),
103.05 (C-1), 75.35 (C-5), 73.22 (C-4), 70.69 (C-2), 68.18 (C-3), 66.43
(C-1′′), 60.45 (C-6).
1H NMR (600 MHz, DMSO-d6): δ = 7.68 (s, 1 H, 7′-H), 7.20 (s, 1 H, 4′-
H), 6.24 (mc, 2 H, 2′-H), 4.88–4.81 (m, 2 H, 1′′-Ha, 2-OH), 4.77–4.70 (m,
3
3
2 H, 1′′-Hb, 4-OH), 4.67 (d, J1,2 = 1.6 Hz, 1 H, 1-H), 4.58 (d, J3-OH,3
=
5.9 Hz, 1 H, 3-OH), 3.68 (td, 3J2,3 = 3.9 Hz, 3J2,1 = 1.7 Hz, 1 H, 2-H), 3.47
3
3
3
(ddd, J3,4 = 9.4 Hz, J3,3-OH = 5.9 Hz, J3,2 = 3.4 Hz, 1 H, 3-H), 3.39 (dq,
3J5,4 = 9.5, 3J5,6 = 6.2 Hz, 1 H, 5-H), 3.20 (td, 3J4,5 = 9.3 Hz, 3J4,3 = 9.3 Hz,
3J4,4-OH = 5.6 Hz, 1 H, 4-H), 1.13 (d, 3J6,5 = 6.1 Hz, 3 H, 6-H).
13C NMR (151 MHz, DMSO-d6): δ = 152.02 (C-7a), 146.89 (C-3a),
141.14 (C-6′), 131.20 (C-5′), 107.49 (C-4′), 105.21 (C-7′), 103.44 (C-2′),
100.05 (C-1), 71.87 (C-4), 70.73 (C-3), 70.28 (C-2), 68.98 (C-5), 65.14
(C-1′′), 17.90 (C-6).
HRMS (ESI, + mode): m/z [M + Na]+ calcd for C14H17NO10Na: 382.0750;
found: 382.0747.
UV/Vis (H2O): λmax (ε) = 245 (10561), 356 nm (5757).
HRMS (ESI,
380.09575; found: 380.09516.
+ mode): m/z [M +
Na]+ calcd for C15H19NO9Na:
6-Nitropiperonyl β-D-Glucopyranoside and 6-Nitropiperonyl α-D-
Glucopyranoside (6b) [cGlucose]
UV/Vis (MeOH): λmax (ε) = 242 (9301), 293 (2365), 344 nm (4377).
Compound 6b was synthesized according to general procedure C over
two steps from 1b (500 mg, 1.22 mmol) as a light yellow solid; yield:
197 mg (0.55 mmol, 45%).
1-(6-Nitro-1,3-benzodioxol-5-yl)ethyl β-L-Rhamnopyranoside (7c)
[cMeRhamnose]
Compound 7c was synthesized according to general procedure C over
two steps from 1c (500 mg, 2.83 mmol) as a light-yellow-brownish
solid; yield: 278 mg (0.78 mmol, 55%); mp 112 °C.
β/α-Anomers
Mp 153 °C; [α]D20 –4.1 (c 0.4, DMSO).
IR (ATR): 3336, 2921, 1617, 1505, 1482, 1482, 1448, 1423, 1382, 1325,
IR (ATR): 3436, 2976, 2935, 1619, 1516, 1502, 1483, 1424, 1397, 1362,
1339, 1255, 1136, 1122, 1109, 1090, 1064, 1029, 999, 933, 904, 882,
1258, 1197, 1166, 1056, 1024, 925, 894, 818, 776, 756, 725 cm–1
.
HRMS (ESI,
382.07502; found: 382.07457.
+ mode): m/z [M +
Na]+ calcd for C14H17NO10Na:
857, 844, 807, 767, 757, 663 cm–1
.
1H NMR (600 MHz, DMSO-d6): δ = 7.53 (s, 1 H, 7′-H), 7.19 (s, 1 H, 4′-
H), 6.23 (mc, 2 H, 2′-H), 5.12 (q, 3J1′′,2′′ = 6.3 Hz, 1 H, 1′′-H), 4.77 (d, 3J2-OH,2
= 4.4 Hz, 1 H, 2-OH), 4.74–4.68 (m, 2 H, 1-H, 4-OH), 4.58–4.51 (m, 1 H,
3-OH), 3.70–3.61 (m, 1 H, 2-H), 3.39–3.30 (m, 1 H, 3-H), 3.11 (mc, 1 H,
UV/Vis (H2O): λmax (ε) = 245 (4078), 356 nm (2340).
β-Anomer
3
3
3
1H NMR (600 MHz, DMSO-d6): δ = 7.70 (s, 1 H, 7′-H), 7.60 (s, 1 H, 4′-H),
6.24 (s, 2 H, 2′-H), 5.36 (d, J = 4.9 Hz, 1 H, 3-/4-OH), 5.08 (d, J1''a,1''b
4-H), 2.89 (dq, J5,4 = 12.2 Hz, J5,6 = 6.5 Hz, 1 H, 5-H), 1.43 (d, J2′′,1′′
=
6.4 Hz, 3 H, 2′′-H), 0.84 (d, 3J6,5 = 6.2 Hz, 3 H, 6-H).
2
=
13C NMR (151 MHz, DMSO-d6): δ = 151.67 (C-7a), 146.63 (C-3a),
141.07 (C-6′), 136.17 (C-5′), 106.58 (C-4′), 104.08 (C-7′), 103.27 (C-2′),
99.63 (C-1), 71.61 (C-4), 70.62 (C-3), 70.55 (C-2), 69.29 (C-5), 69.18
(C-1′′), 22.12 (C-2′′), 17.47 (C-6).
16.2 Hz, 1 H, 1′′-Ha), 5.01–4.88 (m, 3 H, 1′′-Hb, 2-OH, 3-/4-OH), 4.53 (t,
3J6-OH,6a = 5.8 Hz, 3J6-OH,6b = 5.8 Hz, 1 H, 6-OH), 4.27 (d, 3J1,2 = 7.6 Hz, 1 H,
1-H), 3.68 (dd, 2J6a,6b = 11.5 Hz, 3J6a,5 = 5.9 Hz, 1 H, 6-Ha), 3.45 (m, 1 H,
6-Hb), 3.21–3.14 (m, 1 H, 5-H), 3.14–3.05 (m, 3 H, 2-H, 3-H, 4-H).
13C NMR (151 MHz, DMSO-d6): δ = 152.59 (C-7a), 146.58 (C-3a),
140.18 (C-6′), 133.11 (C-5′), 107.18 (C-4′), 105.02 (C-7′), 103.41 (C-2′),
102.43 (C-1), 76.94 (C-3/4), 76.52 (C-5), 73.61 (C-3/4), 69.99 (C-2),
66.54 (C-1′′), 60.97 (C-6).
HRMS (ESI, + mode): m/z [M + Na]+ calcd for C14H17NO9Na: 366.0801;
found: 366.0795.
UV/Vis (H2O): λmax (ε) = 248 (6794), 355 nm (3295).
6-Nitropiperonyl β-D-Lactopyranoside and 6-Nitropiperonyl α-D-
Lactopyranoside (6e) [cLactose]
α-Anomer
1H NMR (600 MHz, DMSO-d6): δ = 7.70 (s, 1 H, 7′-H), 7.57 (s, 1 H, 4′-
H), 6.24 (s, 2 H, 2′-H), 5.03 (d, J = 6.0 Hz, 1 H, 3-/4-OH), 5.01–4.88 (m,
1 H, 1′′-Ha), 4.88–4.73 (m, 4 H, 1′′-Hb, 1-H, 2-OH, 3-/4-OH), 4.49 (t,
Compound 6e was synthesized according to general procedure C over
two steps from 1e (500 mg, 0.71 mmol) as a light yellow solid; yield:
186 mg (0.36 mmol, 50%).
3J6-OH,6a = 5.5 Hz, J6-OH,6b = 5.8 Hz, 1 H, 6-OH), 3.62 (dd, J6a,6b = 11.5
3
2
3
Hz, J6a,5 = 5.9 Hz, 1 H, 6-Ha), 3.54 (mc, 1 H, 3-H), 3.39 (mc, 1 H, 4-H),
β/α-Anomer
mp 203 °C; [α]D20 –16 (c 0.2, MeOH).
3.30–3.24 (m, 1 H, 2-H), 3.14–3.05 (m, 2 H, 6-Hb, 5-H).
13C NMR (151 MHz, DMSO-d6) : δ = 152.59 (C-7a), 146.58 (C-3a),
140.25 (C-6′), 133.11 (C-5′), 107.13 (C-4′), 104.90 (C-7′), 103.29 (C-2′),
98.55 (C-1), 73.34 (C-4), 73.32 (C-3), 71.97 (C-2), 70.28 (C-5), 65.00
(C-1′′), 60.90 (C-6).
IR (ATR): 3367, 1617, 1506, 1487, 1448, 1381, 1323, 1262, 1027, 927,
878, 782, 756 cm–1
HRMS (ESI, mode): m/z [M
544.12784; found: 544.12736.
.
+
+
Na]+ calcd for C20H27NO15Na:
6-Nitropiperonyl β-L-Rhamnopyranoside (6c) [cRhamnose]
UV/Vis (H2O): λmax (ε) = 245 (9206)*, 356 nm (4962).
Compound 6c was synthesized according to general procedure C over
two steps from 1c (500 mg, 2.83 mmol) as a light yellow solid; yield:
233 mg (0.68 mmol, 48%); mp 157 °C; [α]D20 +20 (c 0.2, MeOH).
β-Anomer
1H NMR (600 MHz, DMSO-d6): δ = 7.71 (s, 1 H, 7′′-H), 7.60 (s, 1 H, 4′′-
H), 6.24 (s, 2 H, 2′′-H), 5.52 (d, J = 5.1 Hz, 1 H, OH), 5.07–5.05 (m, 2 H,
1′′′-Ha, OH), 4.94 (mc, 1 H, 1′′′-Hb), 4.82–4.75 (m, 1 H, 6′-OH), 4.72–
4.69 (m, 1 H, OH), 4.67 (t, J = 5.2 Hz, 1 H, OH), 4.61 (t, J = 6.0 Hz, 1 H, 6-
OH), 4.52 (d, J = 4.6 Hz, 1 H, OH), 4.36 (d, 3J1,2 = 4.3 Hz, 1 H, 1-H), 4.21
IR (ATR): 3283, 2917, 1617, 1542, 1517, 1506, 1486, 1447, 1425, 1407,
1323, 1259, 1109, 1127, 1072, 1052, 1022, 979, 927, 915, 870, 815,
755, 686 cm–1
.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, A–K