Pure 8c was obtained as a white solid (1.1 g, 72%). Rf = 0.34
in 15% MeOH/DCM; mp = 199-201 ˚C (dec.); []2D0 = –11.6 (c =
1.0, MeOH); IR (KBr DRIFT) max = 1750 (C=O), 1585 (C=N),
1430, 1368, 1235, 1061 cm-1; 1H-NMR (300 MHz, CD3OD) (300
K): δ 7.28-7.17 (m, 5H, ArH), 5.32 (t, J2,3 = J3,4 = 9.3 Hz, 1H,
H3), 5.27 (d, J1,2 = 10.2 Hz, 1H, H1), 5.02-4.92 (m, 2H, H2 and
H4), 4.20-4.04 (m, 2H, H6a and H6b), 3.94-3.88 (m, 1H, H5),
3.09-2.89 (m, 4H, PhCH2CH2), 2.01, 1.99, 1.95, 1.81 (4 s, 12H,
CH3COO); 13C-NMR (75 MHz, CD3OD) (300 K): δ 170.4, 169.7,
169.5, 169.1 (4 CH3COO), 156.9 (C=N), 140.4 (C-1 of Ph),
127.9 (C-3, C-5 of Ph), 127.9 (C-2, C-6 of Ph), 125.6 (C-4 of
Ph), 78.9 (C-1), 75.1 (C-5), 73.2 (C-3), 69.5 (C-2), 67.8 (C-4),
61.7 (C-6), 33.6 (PhCH2CH2), 32.5 (PhCH2CH2), 18.8(2), 18.6(2)
(4 CH3COO); HRMS-FTMS (ESI) m/z for C23H28O13NS2 [M-
K]-, calcd 590.1008 found 590.0989.
MHz, CD3OD) (300 K): δ 7.66 (d, J = 8.7 Hz, 2H, H3’ and H5’-
Ph-H), 7.25 (d, J = 8.7 Hz, 2H, H2’ and H6’-Ph-H), 5.12 (t, J2,3
=
J3,4 = 9.0 Hz, 1H, H3), 4.99-4.92 (m, 2H, H2 and H4), 4.69 (d,
J1,2 = 10.2 Hz, 1H, H1), 4.19 (dd, J5,6b = 9.3 Hz, J6a,6b = 12.6 Hz,
1H, H6b), 3.98 (dd, J5,6a = 2.1 Hz, J6a,6b = 12.6 Hz, 1H, H6a),
3.26-3.24 (m, 1H, H5), 2.30 (s, 3H, CH3CO2Ph), 2.06, 2.02, 1.94,
1.92 (4 s, 12H, CH3COO); 13C-NMR (75 MHz, CD3OD) (300
K): δ 169.4 (CH3COOPh), 168.5, 168.3, 168.2, 168.1 (4
CH3COO), 155.0 (C=N), 150.9 (C-4 of Ph), 128.9 (C-3, C-5 of
Ph), 127.9 (C-1 of Ph), 120.2 (C-2, C-6 of Ph), 79.7 (C-1), 73.9
(C-5), 72.1 (C-3), 68.4 (C-2), 66.3 (C-4), 59.9 (C-6), 18.0
(CH3COOPh), 17.8, 17.7, 17.6(2) (4 CH3COO); HRMS (ESI)
m/z for C23H26O15NS2 [M-K]-, calcd 620.0749 found 620.0728.
4.5.7. Potassium 2,3,4,6-Tetra-O-acetyl-2,3-
dichlorophenylglucosinolate 8g.
4.5.4. Potassium 2,3,4,6-Tetra-O-acetyl-(2-
phenylethenyl)glucosinolate 8d.
Pure 8g was obtained as a white solid (0.78 g, 81%). Rf = 0.31
in 15% MeOH/DCM; mp = 142-144 ˚C (dec.); []2D0 = +15 (c =
1.0, MeOH); IR (KBr DRIFT) max = 2942, 2884, 1754 (C=O),
Pure 8d was obtained as a white solid (1.13 g, 83%). Rf = 0.29
in 15% MeOH/DCM ; mp = 124-125 ˚C (dec.); []2D0 = –13.8 (c =
1.0, MeOH); IR (KBr DRIFT) max = 2942, 1749 (C=O), 1627,
1
1650, 1572, 1505, 1413, 1396, 1217, 1062 cm-1; H-NMR (300
MHz, CD3OD) (300 K): δ 7.73-7.69 (m, 1H, H4’-Ph-H), 7.49-
7.43 (m, 2H, H5’ and H6’-Ph-H), 5.12 (t, J2,3 = J3,4 = 9.3 Hz, 1H,
H3), 4.97-4.91 (m, 2H, H2 and H4), 4.37 (d, J1,2 = 10.2 Hz, 1H,
H1), 4.11 (dd, J5,6b = 4.2 Hz, J6a,6b = 12.6 Hz, 1H, H6b), 3.90 (dd,
J5,6a = 2.4 Hz, J6a,6b = 12.6 Hz, 1H, H6a), 3.06-3.01 (m, 1H, H5),
2.06, 2.02, 1.92, 1.92 (4 s, 12H, CH3COO); 13C-NMR (75
MHz, CD3OD) (300 K): δ 170.4, 169.7, 169.3, 169.1 (4
CH3COO), 154.7 (C=N), 132.8 (C-3 of Ph), 131.8 (C-4 of Ph),
131.8 (C-1 of Ph), 131.7 (C-2 of Ph), 129.8 (C-6 of Ph), 127.2
(C-5 of Ph), 80.5 (C-1), 74.9 (C-5), 73.0 (C-3), 69.0 (C-2), 67.3
(C-4), 60.8 (C-6), 18.9, 18.8, 18.7(2) (4 CH3COO); HRMS
(ESI) m/z for C21H22O13Cl2NS2 [M-K]-, calcd 629.9915 found
629.9971.
1
1539 (C=N), 1447, 1370, 1230, 1058 cm-1; H-NMR (300 MHz,
CD3OD) (300 K): δ 7.58-7.55 (m, 2H, H2’ and H6’-Ph-H), 7.41-
7.32 (m, 4H, H3’, H4’, H5’-Ph-H and PhCH=CH), 6.93 (d, J =
15.9 Hz, 1H, PhCH=CH), 5.38-5.31 (m, 2H, H1 and H3), 5.08-
5.00 (m, 2H, H2 and H4), 4.26 (dd, J5,6b = 5.4 Hz, J6a,6b = 12.3
Hz, 1H, H6b), 4.12 (dd, J5,6a = 2.1 Hz, J6a,6b = 12.3 Hz, 1H, H6a),
4.00-3.94 (m, 1H, H5), 2.02, 1.99, 1.95, 1.90 (4 s, 12H,
CH3COO); 13C-NMR (75 MHz, CD3OD) (300 K): δ 170.5, 169.7,
169.5, 169.4 (4 CH3COO), 154.1 (C=N), 137.9 (PhCH=CH),
135.1 (C-1 of Ph), 128.8 (C-4 of Ph), 128.3 (C-3, C-5 of Ph),
126.9 (C-2, C-6 of Ph), 118.8 (PhCH=CH), 80.3 (C-1), 75.1 (C-
5), 73.3 (C-3), 69.9 (C-2), 67.9 (C-4), 61.7 (C-6), 18.8(2), 18.7(2)
(4 CH3COO); HRMS-FTMS (ESI) m/z for C23H26O13NS2 [M-
K]-, calcd 588.0851 found 588.0835.
4.5.8. Potassium 2,3,4,6-Tetra-O-acetyl-4-
bromophenylglucosinolate 8h.
4.5.5. Potassium 2,3,4,6-Tetra-O-acetyl-3,4-
dimethoxyphenylglucosinolate 8e.
Pure 8h was obtained as a white solid (1.27 g, 85%). Rf = 0.26
in 15% MeOH/DCM mp = 135-136 ˚C (dec.); []2D0 = +28.3 (c =
1.0, MeOH); IR (KBr DRIFT) max = 2937, 2873, 1750 (C=O),
Pure 8e was obtained as a white solid (1.24 g, 68%). Rf = 0.72
in 10% MeOH/DCM; mp = 114-115 ˚C (dec.); []2D1 = +5 (c =
1.0, MeOH); IR (KBr DRIFT) max = 2944 (CH3), 1746 (C=O),
1599 (C=N), 1514, 1247, 1062, cm-1; 1H-NMR (300 MHz,
CD3OD) (300 K): δ 7.26-7.21 (m, 2H, H2’ and H6’- Ph-H), 7.05
(d, J5’,6 = 5.4 Hz, 1H, H5’-Ph-H), 5.14 (t, J2,3 = J3,4 = 9.0 Hz, 1H,
H3), 5.00-4.94 (m, 2H, H2 and H4), 4.87 (d, J1,2 = 10.2 Hz, 1H,
H1), 4.19 (dd, J5,6b = 4.2 Hz, J6a,6b = 12.6 Hz, 1H, H6b), 4.03 (dd,
J5,6a = 2.4 Hz, J6a,6b = 12.6 Hz, 1H, H6a), 3.87 (s, 6H, 2
CH3OPh), 3.42-3.37 (m, 1H, H5), 2.04, 2.03, 1.94 1.93 (4 s,
12H, CH3COO); 13C-NMR (75 MHz, CD3OD) (300 K): δ 170.5,
169.7, 169.4, 169.3 (4 CH3COO), 155.9 (C=N), 150.9 (C-4 of
Ph), 148.6 (C-3 of Ph), 124.1 (C-1 of Ph), 121.9 (C-2 of Ph),
112.2 (C-5 of Ph), 110.5 (C-6 of Ph), 81.5 (C-1), 75.2 (C-5), 73.3
(C-3), 69.9 (C-2), 67.5 (C-4), 61.1 (C-6), 55.0, 54.8 (2
CH3OPh), 18.9(2), 18.7(2) (4 CH3COO); HRMS (ESI) m/z for
C23H28O15NS2 [M-K]-, calcd 622.0906, found 622.0998.
1
1585 (C=N), 1485, 1430, 1368, 1235, 1063 cm-1; H-NMR (300
MHz, CD3OD) (300 K): δ 7.67-7.64 (m, 2H, H3’ and H5’-Ph-H),
7.59-7.54 (m, 2H, H2’ and H6’-Ph-H), 5.16 (t, J2,3 = J3,4 = 9.0
Hz, 1H, H3), 5.00-4.92 (m, 2H, H2 and H4), 4.78 (d, J1,2 = 10.2
Hz, 1H, H1), 4.18 (dd, J5,6b = 4.8 Hz, J6a,6b = 12.6 Hz, 1H, H6b),
3.98 (dd, J5,6a = 2.4 Hz, J6a,6b = 12.6 Hz, 1H, H6a), 3.39-3.34 (m,
1H, H5), 2.07, 2.03, 1.95, 1.92 (4 s, 12H, CH3COO); 13C-NMR
(75 MHz, CD3OD) (300 K): δ 170.4, 169.6, 169.4, 169.2 (4
CH3COO), 155.3 (C=N), 131.1 (C-3, C-5 of Ph), 130.9 (C-4 of
Ph), 130.4 (C-2, C-6 of Ph), 124.2 (C-1 of Ph), 80.9 (C-1), 75.1
(C-5), 73.2 (C-3), 69.6 (C-2), 67.5 (C-4), 61.1 (C-6), 18.9, 18.8,
18.7(2) (4 CH3COO); HRMS (ESI) m/z for C21H23O13BrNS2
[M-K]-, calcd 639.9800 found 639.9937.
4.6. General procedure for the preparation of glucosinolates (9a-
h).
To a solution of O-acetylglucosinolate 8 in anhydrous MeOH
(20 ml) under a N2 atmosphere was added dry MeOK (0.4 eq.)
until pH = 8-9 was reached. After stirring for 3 h at rt, the
solution was made neutral by the addition of glacial acetic acid
then the solution was concentrated under reduced pressure. The
GLs 9a-h were obtained by flash chromatography eluting with
EtOAc:MeOH:H2O (16:4:1).
4.5.6. Potassium 2,3,4,6-Tetra-O-acetyl-4-acetyl-O-
phenylglucosinolate 8f.
Pure 8f was obtained as a white solid (0.76 g, 72%). Rf = 0.48
in 20% MeOH/DCM; mp = 129-131 ˚C (dec.); []2D1 = –20 (c =
1.0, MeOH); IR (KBr DRIFT) max = 2939 (CH3), 1747 (C=O),
1
1599 (C=N), 1504, 1433, 1371, 1230, 1061 cm-1; H-NMR (300