0.026 mmol), 4-dimethylaminopyridine (0.013 mmol),
triethylamine (0.26 mmol), and substituted acid chloride (0.13
mmol). Isolated PTL-14-15: 4 mg, 36 % yield. H NMR (400
2.59-2.45 (m, 1H), 2.34-2.32 (m, 1H), 2.24-2.18 (m, 3H), 2.03-
1.97 (m, 2H), 1.38-1.28 (m, 4H) ppm, 13C NMR (125 MHz,
CDCl3): δ = 169.1, 158.4, 154.3,139.0, 133.0, 132.4, 132.0,
130.5, 129.3, 126.8, 121.4, 120.0, 114.7, 112.1, 82.2, 66.2, 62.2,
61.1, 47.3, 46.0, 37.1, 36.2, 31.5, 24.2, 16.9 ppm, MS (ESI) calcd
for C27H25F3O6 [M+Na]+ m/z: 525.1; found: 525.0.
1
MHz, CDCl3): δ = 8.13 (d, J = 7.6 Hz, 1H), 7.74 (s, 1H), 7.37-
7.27 (m, 3H), 6.34 (d, J = 3.6 Hz, 1H), 5.61 (d, J = 2.8 Hz, 1H),
5.55 (dd, J = 4.0, 9.6 Hz, 1H), 5.10 (d, J = 12 Hz, 1H), 4.85 (d, J
= 12 Hz, 1H), 3.93 (t, J = 8.8 Hz, 1H), 3.84 (s, 3H), 2.82-2.78 (m,
3H), 2.64-2.59 (m, 1H), 2.36-2.13 (m, 4H), 1.88-1.84 (m, 1H),
1.33 (s, 3H), 1.30-1.08 (m,1H) ppm, 13C NMR (125 MHz,
CDCl3): δ = 178.2, 169.1, 151.1, 139.0, 137.2, 135.1, 134.2,
131.2,123.0, 122.1, 121.5, 116.1, 109.9, 82.4, 66.2, 61.1, 59.9,
47.3, 36.5, 36.2, 33.5, 31.1, 23.9, 17.0 ppm, MS (ESI) calcd for
C25H27NO5 [M+Na]+ m/z: 444.2; found: 444.3.
4.4.10. (3aR,5S,9aR,10aS,10bS,E)-6,9a-dimethyl-3-methylene-
2-oxo-2,3,3a,4,5,8,9,9a,10a,10b-decahydrooxireno[2',3':9,10]
cyclodeca[1,2-b]furan-5-yl
5-(4-chlorophenyl)isoxazole-3-
carboxylate (11): Standard procedure was applied using 9(S)-
hydroxy-parthenolide (2) (10 mg, 0.037 mmol), 4-
dimethylaminopyridine (0.018 mmol), triethylamine (0.37
mmol), and substituted acid chloride (0.18 mmol). Isolated PTL-
9-19: 9 mg, 47 % yield. 1H NMR (400 MHz, CDCl3): δ = 7.75 (d,
J = 8.0 Hz, 2H), 7.48 (d, J = 8.4 Hz, 2H), 6.90 (s, 1H), 6.38 (s,
1H), 5.71 (s, 1H), 5.65 (d, J = 10.8 Hz, 1H), 5.52 (d, J = 10.8 Hz,
1H), 3.92 (t, J = 8.8 Hz, 1H), 2.99 (brs, 1H), 2.75 (d, J = 8.8 Hz,
1H), 2.57-2.18 (m, 5H), 1.84 (s, 3H), 1.38-1.27 (m, 4H) ppm, 13C
NMR (125 MHz, CDCl3): δ = 170.8, 168.4, 158.8, 156.7, 137.7,
137.1, 132.3, 129.5, 129.0, 127.2, 124.9, 122.1, 100.2, 82.5, 81.3,
65.9, 61.3, 44.0, 35.9, 35.7, 23.8, 17.3, 11.8 ppm, MS (ESI) calcd
for C25H24ClNO6 [M+Na]+ m/z: 492.1; found: 492.1.
4.5.7. ((3aR,9aR,10aS,10bS,Z)-9a-methyl-3-methylene-2-oxo-
2,3,3a,4,5,8,9,9a,10a,10b-
decahydrooxireno[2',3':9,10]cyclodeca
[1,2-b]furan-6-
yl)methyl thiophene-2-carboxylate (8): Standard procedure was
applied using 14-hydroxy-parthenolide (3) (8 mg, 0.030 mmol),
4-dimethylaminopyridine (0.015 mmol), triethylamine (0.30
mmol), and substituted acid chloride (0.15 mmol). Isolated PTL-
1
14-16: 6 mg, 53 % yield. H NMR (400 MHz, CDCl3): δ = 7.80
(d, J = 3.6 Hz, 1H), 7.57 (d, J = 4.8 Hz, 1H), 7.12 (t, J = 4.8 Hz,
1H), 6.35 (d, J = 3.2 Hz, 1H), 5.63 (d, J = 2.8 Hz, 1H), 5.56 (dd, J
= 3.6, 8.8 Hz, 1H), 4.98 (d, J = 12 Hz, 1H), 4.85 (d, J = 12 Hz,
1H), 3.97 (t, J = 8.8 Hz, 1H), 2.84-2.80 (m, 2H), 2.69-2.78
(m,1H), 2.63-2.52 (m, 1H), 2.41-2.32 (m, 3H), 2.24-2.17 (m,1H),
2.01-1.82 (m, 1H), 1.33-1.29 (m, 4H) ppm, 13C NMR (125 MHz,
CDCl3): δ = 169.1, 161.9, 139.0, 133.9, 133.1, 132.9, 132.7,
132.2, 128.0, 121.5, 82.5, 66.2, 62.3, 61.0, 47.2, 36.9, 36.2, 31.7,
24.1,16.9 ppm, MS (ESI) calcd for C20H22O5S [M+Na]+ m/z:
397.1; found: 397.2.
4.4.11.
((3aR,9aR,10aS,10bS,Z)-9a-methyl-3-methylene-2-
oxo-2,3,3a,4,5,8,9,9a,10a,10b-
decahydrooxireno[2',3':9,10]cyclodeca
[1,2-b]furan-6-
yl)methyl 5-(4-chlorophenyl)isoxazole-3-carboxylate (12):
Standard procedure was applied using 14-hydroxy-parthenolide
(3) (10 mg, 0.037 mmol), 4-dimethylaminopyridine (0.018
mmol), triethylamine (0.37 mmol), and substituted acid chloride
1
(0.18 mmol). Isolated PTL-14-19: 9 mg, 47 % yield. H NMR
(400 MHz, CDCl3): δ = 7.73 (d, J = 8.4 Hz, 2H), 7.48 (d, J = 8.8
Hz, 2H), 6.90 (s, 1H), 6.35 (s, 1H), 5.62 (s, 1H), 5.58 (brs, 1H),
5.08 (d, J =12 Hz, 1H), 4.93 (d, J = 12 Hz, 1H), 4.02 (t, J = 8.4
Hz, 1H), 2.84-2.79 (m, 2H), 2.73-2.70 (m, 1H), 2.61-2.52
(m,1H), 2.36-2.34 (m, 1H), 2.25-2.19 (m, 3H), 2.07-1.95 (m,1H),
1.38-1.33 (m, 1H), 1.24 (s, 3H) ppm, 13C NMR (125 MHz,
CDCl3): δ = 170.8, 169.1, 159.8, 156.5, 138.9, 137.1, 133.1,
132.3, 129.5, 127.1, 124.8, 121.5, 100.1, 82.1, 66.3, 62.9, 61.0,
47.3, 36.9, 36.1, 31.3, 24.2, 16.9 ppm, MS (ESI) calcd for
C25H24ClNO6 [M+Na]+ m/z: 492.12; found: 492.3.
4.4.8. ((3aR,9aR,10aS,10bS,Z)-9a-methyl-3-methylene-2-oxo-
2,3,3a,4,5,8,9,9a,10a,10b-
decahydrooxireno[2',3':9,10]cyclodeca
yl)methyl
[1,2-b]furan-6-
(9):
5-(4-bromophenyl)furan-2-carboxylate
Standard procedure was applied using 14-hydroxy-parthenolide
(3) (10 mg, 0.037 mmol), 4-dimethylaminopyridine (0.018
mmol), triethylamine (0.37 mmol), and substituted acid chloride
1
(0.18 mmol). Isolated PTL-14-17: 6 mg, 31 % yield. H NMR
(400 MHz, CDCl3): δ = 7.57-7.52 (m, 4H), 7.24 (d, J = 3.2 Hz,
1H), 6.74 (d, J = 3.6 Hz, 1H), 6.37 (d, J = 3.2 Hz, 1H), 5.63 (d, J
=2.4 Hz, 1H), 5.58 (dd, J = 3.6, 8.8 Hz, 1H), 4.98 (d, J =12.0 Hz,
1H), 4.90 (d, J= 12 Hz, 1H), 4.0 (t, J= 8.4 Hz, 1H), 2.85-2.81 (m,
2H), 2.71-2.68 (m, 1H), 2.55-2.47 (m, 1H), 2.35-2.32 (m, 1H),
2.25-2.20 (m, 3H), 2.07-1.98 (m, 1H), 1.37-1.29 (m, 4H) ppm,
13C NMR (125 MHz, CDCl3): δ = 169.0, 158.4, 156.8, 143.4,
139.0, 132.9, 132.5, 132.1, 128.1, 126.1, 123.4, 121.5, 120.5,
107.4, 82.2, 66.2, 62.0, 61.1, 47.3, 37.0, 36.2, 31.6, 24.1, 16.9
ppm, MS (ESI) calcd for C26H25BrO6 [M+Na]+ m/z: 535.1; found:
535.2.
4.4.12.
((3aR,9aR,10aS,10bS,Z)-9a-methyl-3-methylene-2-
oxo-2,3,3a,4,5,8,9,9a,10a,10b-
decahydrooxireno[2',3':9,10]cyclodeca
[1,2-b]furan-6-
yl)methyl
3-(4-bromophenyl)-1H-pyrazole-5-carboxylate
(13): Standard procedure was applied using 9(S)-hydroxy-
parthenolide (2) (10 mg, 0.030 mmol), 4-dimethylaminopyridine
(0.015 mmol), triethylamine (0.30 mmol), and substituted acid
chloride (0.15 mmol). Isolated PTL-14-13: 8 mg, 41 % yield. 1H
NMR (400 MHz, CDCl3): δ = 7.60-7.54 (m, 4H), 7.05 (s, 1H),
6.33 (brs, 1H), 5.61-5.56 (m, 2H), 5.06 (d, J = 12 Hz, 1H), 4.84
(d, J = 12 Hz, 1H), 4.03-3.99 (m, 1H), 2.83-2.81 (m, 2H), 2.76-
2.67 (m, 1H), 2.61-2.53 (m, 1H), 2.51-2.50 (m, 1H), 2.35-2.16
(m, 3H), 1.89-1.84 (m, 1H), 1.59-1.46 (m, 1H), 1.39-1.25 (m,
4H) ppm, 13C NMR (125 MHz, CDCl3): δ = 169.4, 160.5, 138.9,
132.8, 132.7, 132.1, 129.3, 127.4, 127.2, 122.8, 121.7, 105.7,
82.2, 66.2, 61.8, 61.2, 47.2, 36.6, 36.1, 31.2, 24.1, 17.0, MS
(ESI) calcd for C25H25BrN2O5[M+Na]+ m/z: 535.1; found: 535.0.
4.4.9. ((3aR,9aR,10aS,10bS,Z)-9a-methyl-3-methylene-2-oxo-
2,3,3a,4,5,8,9,9a,10a,10b-
decahydrooxireno[2',3':9,10]cyclodeca
[1,2-b]furan-6-
yl)methyl 5-(2-(trifluoromethyl)phenyl)furan-2-carboxylate
(10): Standard procedure was applied using 14-hydroxy-
parthenolide (3) (10 mg, 0.037 mmol), 4-dimethylaminopyridine
(0.018 mmol), triethylamine (0.37 mmol), and substituted acid
chloride (0.18 mmol). Isolated PTL-14-18: 7 mg, 37 % yield. 1H
NMR (400 MHz, CDCl3): δ = 7.78 (d, J = 7.6 Hz, 1H), 7.71 (d, J
= 7.6 Hz, 1H), 7.62 (t, J = 8.0 Hz, 1H), 7.53 (t, J = 6.8 Hz, 1H),
7.28-7.25 (m, 1H), 6.78 (s, 1H), 6.32 (d, J = 2.8 Hz, 1H), 5.59-
5.54 (m, 2H), 4.99 (d, J =12 Hz, 1H), 4.89 (d, J = 12 Hz, 1H),
3.97 (t, J = 8.8 Hz, 1H), 2.82-2.79 (m, 1H), 2.71-2.68 (m, 1H),
4.4.13.
(3aR,9aR,10aS,10bS,Z)-6-((benzyloxy)methyl)-9a-
methyl-3-methylene-3a,4,5,8,9,9a,10a,10b-
octahydrooxireno[2',3':9,10] cyclodeca[1,2-b]furan-2(3H)-one
(14):Standard procedure was applied using 14-hydroxy-
parthenolide (3) (10 mg, 0.037 mmol), Ag2O (18 mg, 0.074