The Total Syntheses of Basiliolide C, epi-Basiliolide C, and...
Transcript of The Total Syntheses of Basiliolide C, epi-Basiliolide C, and...
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The Total Syntheses of Basiliolide C, epi-Basiliolide C, and Protecting-Group-Free Total Syntheses of Transtaganolides C and D ** Jonny R. Gordon, Hosea M. Nelson, Scott C. Virgil and Brian M. Stoltz*
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Table of Contents I. Materials and Methods S3 II. Organozinc Cross-Coupling Optimization S4 III. Comparison of Spectral Data for Synthetic and S5 Reported Basiliolide C (8), Transtaganolide C (4), and Transtaganolide D (5) IV. Bioactivity of Synthetic Transtaganolide C (4) S11 V. Spectra S12
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I. Materials and Methods Unless otherwise stated, reactions were performed in flame-dried glassware under an argon or nitrogen atmosphere using dry deoxygenated solvents. Solvents were dried by passage through an activated alumina column under argon. Pd(PPh3)4 was prepared using known methods. Thin layer chromatography (TLC), both preparatory and analytical, was visualized by UV fluorescence quenching, p-anisaldehyde, I2, or KMnO4 staining. Analytical super critical fluid chromatography (SFC) was performed using an SFC and AD-H column. Preparatory SFC was performed with a SFC and a prep AD-H column (21 x 250 mm, 5mic part#19445). Silica gel (particle size 0.032-0.063 mm) was used for flash chromatography. 1H NMR and 13C NMR spectra were recorded at 300 MHz or 500 MHz. 1H NMR spectra are reported relative to CDCl3 (7.26 ppm). Data for 1H NMR spectra are reported as follows: chemical shift (ppm), multiplicity, coupling constant (Hz), integration. Multiplicities are reported as follows: s = singlet, d = doublet, t = triplet, q = quartet, sept. = septet, m = multiplet, bs = broad singlet. 13C NMR spectra are reported relative to CDCl3 (77.16 ppm). FTIR spectra are reported in frequency of absorption (cm-1). HRMS were acquired using a TOF with a multimode source in electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI), or multimode-ESI/APCI.
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II. Organozinc Cross-Coupling Optimization
Yields of methyl ester 30[1] and consumption of vinyl iodide 28[2] were quantified using the calibration curves (Figure SI-1A and B), which graph the area ratio of GC peaks as a function of the molar ratio of either the methyl ester 30 and the tridecane internal standard or substrate 28 and the tridecane internal standard. This data was collected from several individual GC runs depicted in Table SI-1.
Figure SI-1. (a) Calibration curve used to determine cross-coupling yields comparing methyl ester 30 and tridecane internal standard. (b) Calibration curve used to determine cross-coupling substrate consumption by comparing vinyl iodide 28 and tridecane internal standard. Table SI-1. (a) The molar ratio of product 30 and tridecane with the associated peak area ratio obtained from GC analysis. (b) The molar ratio of substrate 28 and tridecane with the associated peak area ratio obtained from GC analysis.
28
Pd2(dba)3(5 mol%)
ligand(15 mol%)
(27, 1.5 equiv)THF, 30 °C, 3 h
OMeClZn
I
29
OMe
30
OMe
O
0"0.5"1"
1.5"2"
2.5"3"
3.5"4"
4.5"
0" 0.5" 1" 1.5" 2" 2.5"
area ratio
mol
ar ra
tio
y = 1.8184x–0.0611R2 = 0.99933
Curve comparing product (30) and internal standard tridecane
0"0.5"1"
1.5"2"
2.5"3"
3.5"4"
4.5"
0" 0.2" 0.4" 0.6" 0.8" 1" 1.2" 1.4" 1.6" 1.8"
mol
ar ra
tio
area ratio
Curve comparing substrate (28) and internal standard tridecane
y = 2.4601x–0.0062R2 = 0.99967
a) b)
entry area ratio
2
3
4
1
molar ratio
O
OMe
30
tridecane
4 2.217
2 1.169
1
0.3133
0.5758
0.5
5 0.15470.25
entry area ratio
2
3
4
1
molar ratio
4 1.626
2 0.8269
1
0.2134
0.3913
0.5
5 0.10550.25
a) b)
I
28
tridecane
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III. Comparison of Spectral Data for Synthetic and Reported Basiliolide C (8), Transtaganolide C (4), and Transtaganolide D (5)
Table SI-2. Comparison of 1H NMR data for synthetic and reported natural[3] basiliolide C (8).
basiliolide C (8)
OO
MeO
H
O
O
O
12 11
15
13
58
414
63 710
12
9
18
17 19
16
O20
21
Assignment Synthetic 8 (ppm) Multiplicity, J (Hz)
C2 6.05 6.06 dd, 6.4, 1.1
C3 3.29 3.29 d, 6.4
C4 — — —
C5 1.29 dd, 12.9, 4.6
C6 1.75 1.76 dddd, 13.8, 13.0, 12.9, 2.8
1.64–1.50 1.54 dddd, 13.8, 4.6, 3.9, 2.8
C7 1.93 1.94 ddd, 13.7, 3.9, 2.8
1.41 1.42 ddd, 13.7, 13.0, 2.8
1.32–1.24
C1 — ——
C9 3.14 3.15 s
C10 — — —
C11 7.00 7.00 dd, 17.7, 11.1
C12 5.17 dd, 11.0, 1.0
5.06 5.06 dd, 17.7, 1.0
C13 1.23 1.24 s
C14 1.12 1.12 s
C15 3.73 3.74 d, 10.8
5.16
C8 — ——
Multiplicity, J (Hz)Natural 8 (ppm)
C16 — — —
C17 5.00 5.01 d, 1.1
C18 — — —
C19 — — —
C20 — — —
C21 2.08 2.09 s
3.73 3.74 sOMe
3.69 3.70 d, 10.8
dd, 6.5, 1.2
d, 6.5
—
qd, 13.5, 3.0
m
dt, 13.5, 3.4
td, 13.5, 3.0
m
—
s
—
dd, 17.7, 11.1
dd, 17.7, 1.2
s
s
d, 10.8
dd, 11.1, 1.4
—
—
d, 1.4
—
—
—
s
s
d, 10.8
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Table SI-3. Comparison of 13C NMR data for synthetic and reported natural[3] basiliolide C (8).
basiliolide C (8)
OO
MeO
H
O
O
O
12 11
15
13
58
414
63 710
12
9
18
17 19
16
O20
21
Assignment Synthetic 8 (ppm)
C2 123.0 122.8
C3 49.8 49.7
C4 37.1 37.0
C5 44.7
C6 21.2 21.1
C7 40.3 40.2
44.8
C1 138.6138.6
C9 53.4 53.3
C10 87.0 86.9
C11 142.7 142.6
C12 112.3
C13 28.7 28.6
C14 19.8 19.6
C15 70.6 70.4
112.5
C8 38.438.6
Natural 8 (ppm)
C16 170.7 170.7
C17 79.2 79.0
C18 157.0 156.9
C19 162.4 162.3
C20 171.0 170.8
C21 20.9 20.7
56.6 56.4OMe
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Table SI-4. Comparison of 1H NMR data for synthetic and reported natural[4] transtaganolide C (4).
OO
MeO
H
O
O12 16
15
18
58
4
14
63 710
17
9
12
11 19
13
transtaganolide C (4)
Assignment Synthetic 4 (ppm) Multiplicity, J (Hz)
C2 6.07 6.08 dd, 6.5, 1.1
C3 3.06 3.07 d, 6.5
C4 — — —
C5 1.30 dd, 11.5, 6.5
C6 1.71–1.63 1.70–1.60 m
1.71–1.63 1.70–1.60 m
C7 1.48–1.39 1.44 ddd, 13.0, 13.0, 3.3
1.71–1.63 1.65 m
1.34–1.27
C1 — ——
C9 3.23 3.24 s
C10 — — —
C11 5.00 5.01 d, 1.1
C12 — —
C13 — —
C14 0.97 0.98 s
C15 1.08 1.09 s
—
C8 — ——
Multiplicity, J (Hz)Natural 4 (ppm)
C16 5.80 5.81 dd, 17.4, 10.8
C17 5.03 5.05 br d, 10.7
C18 1.60 1.61 s
C19 — — —
3.71 3.72 sOMe
dd, 6.5, 1.5
d, 6.5
—
m
m
m
m
m
—
s
—
d, 1.5
s
s
—
—
dd, 17.5, 11.0
d, 11.0
s
—
s
5.07 5.08 br d, 17.4d, 17.5
——
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Table SI-5. Comparison of 13C NMR data for synthetic and reported natural[4] transtaganolide C (4).
OO
MeO
H
O
O12 16
15
18
58
4
14
63 710
17
9
12
11 19
13
transtaganolide C (4)
Assignment Synthetic 4 (ppm)
C2 123.6 123.5
C3 53.8 53.8
C4 33.3 33.2
C5 47.9
C6 19.9 19.8
C7 38.3 38.3
48.1
C1 131.9138.0
C9 50.6 50.4
C10 87.3 87.4
C11 79.3 79.1
C12 156.7
C13 171.8 172.0
C14 29.9 29.6
C15 24.8 24.8
156.7
C8 38.438.4
Natural 4 (ppm)
C16 146.5 146.5
C17 112.8 112.8
C18 19.2 19.1
C19 162.3 162.5
56.6 56.3OMe
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Table SI-6. Comparison of 1H NMR data for synthetic and reported natural[4] transtaganolide D (5).
OO
MeO
H
O
O12 16
15
18
58
4
14
63 710
17
9
12
11 19
13
transtaganolide D (5)
Assignment Synthetic 5 (ppm) Multiplicity, J (Hz)
C2 6.09 6.08 dd, 6.5, 1.2
C3 3.06 3.04 d, 6.6
C4 — — —
C5 1.34 dd, 12.6, 5.3
C6 1.64 1.65–1.53 m
1.59–1.56 1.65–1.53 m
C7 1.39 1.39 ddd, 13.0, 13.0, 3.3
1.91 1.89 ddd, 13.0, 3.3, 3.3
1.33
C1 — ——
C9 3.13 3.14 s
C10 — — —
C11 5.02 5.02 d, 1.1
C12 — —
C13 — — —
C14 0.97 0.96 s
C15 1.04 1.02 s
—
C8 — ——
Multiplicity, J (Hz)Natural 5 (ppm)
C16 7.00 6.98 dd, 17.8, 11.2
C17 5.15 5.11 dd, 11.1, 1.1
C18 1.22 1.21 s
C19 — — —
3.73 3.72 sOMe
dd, 6.5, 1.0
d, 6.5
—
dquint, 13.5, 3.0
m
dt, 13.5, 3.5
dt, 13.5, 3.5
dd, 13.5, 3.5
—
s
—
d, 1.0
s
s
—
—
dd, 17.5, 11.0
dd, 11.0, 1.0
s
—
s
5.05 5.03 dd, 17.8, 1.1dd, 17.5, 1.0
—
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Table SI-7. Comparison of 13C NMR data for synthetic and reported natural[4] transtaganolide D (5).
OO
MeO
H
O
O12 16
15
18
58
4
14
63 710
17
9
12
11 19
13
transtaganolide D (5)
Assignment Synthetic 5 (ppm)
C2 123.9 123.8
C3 54.0 53.9
C4 33.3 33.2
C5 48.2
C6 20.5 20.3
C7 40.5 40.3
48.4
C1 137.5137.7
C9 53.3 53.1
C10 87.3 87.4
C11 79.4 79.2
C12 156.6
C13 171.7 171.9
C14 29.9 29.8
C15 24.8 24.7
156.7
C8 38.338.4
Natural 5 (ppm)
C16 142.9 142.9
C17 112.1 111.9
C18 28.5 28.4
C19 162.6 162.7
56.3 56.3OMe
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IV. Bioactivity of Synthetic Transtaganolide C (4) Appendino, Muñoz and coworkers assayed naturally isolated transtaganolide C (4) for its effect on calcium mobilization as well as cell viability following exposure to the natural product 4.[5] To ensure the data obtained was not the result of trace thapsigargin (1) contamination in the isolation sample, we sent synthetic transtaganolide C (4) to be tested as a control. Both calcium mobilization (Figure SI-2)[6] and cell viability (Figure SI-3)[6] assays were consistent with those observed with naturally isolated transtaganolide C (4).
Figure SI-2. The effect of synthetic transtaganolide C (4) or naturally isolated thapsigargin (1) on calcium mobilization as a function of time (arrows indicate the time at which a reagent was added).[6]
Figure SI-3. Percentage of cells still viable after 24 hours of exposure to either synthetic transtaganolide C (4) or thapsigargin (1).[6] General procedure for calcium mobilization. Jurkat cells were incubated for 1 h at 37 ºC in Tyrode’s salt solution (137 mM NaCl, 2.7 mM KCl, 1.8 mM CaCl2, 1.0 mM MgCl2, 0.4 mM NaH2PO4, 12.0 mM NaHCO3, 5.6 mM D-glucose) containing 5 µM Indo1-AM (Invitrogen) for 30 minutes at 37 °C in the dark. Cells were then harvested, washed three times with buffer to remove extracellular Indo-1 dye, readjusted to 106 cells/mL in the appropriate buffer and analyzed in a spectrofluorimeter operated in the ratio mode (Hitachi F-2500 model, Hitachi Ltd.) under continuous stirring and at a constant temperature of 37 ºC using a water-
0.9
1.4
1.9
2.4
2.9
3.4
0 50 100 150 200 250 300 350 400 450
Rat
io 3
40/3
80
Basiliolide)1uM)
Thapsigargin)1uM)
Io BSD-A / TG
Time (s)
Rat
io 3
40/3
80
transtaganolide C (4)thapsigargin (1) ionomycin (10 µM)
transtaganolide C (4) 1µM
thapsigargin (1) 1µM
0
20
40
60
80
100
120
- 0,5 1 2,5 5 10 20
% V
IAB
ILIT
Y
BSD$A&(µM)&
0
20
40
60
80
100
120
- 0,5 1 2,5 5 10 20
% V
IAB
ILIT
Y
TG#(µM)#
% V
iabi
lity
% V
iabi
lity
Concentration (µM) Concentration (µM)
transtaganolide C (4) thapsigargin (1)
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jacketed device. After five minutes for accommodation to equilibrate temperatures, samples were excited at 338 nm and emission was collected at 405 and 485 nm, corresponding to the fluorescence emitted by Ca2+-bound and free Indo-1, respectively. [Ca2+]i was calculated using the ratio values between bound- and free-Indo-1 fluorescence, and assuming an Indo-1 Kd for Ca2+ of 0.23 µM. Maximum and minimum ratio values for calculations were determined by the addition at the end of the measurements of 10 µM ionomycin. [Ca2+]i changes are presented as changes in the ratio of bound-to-free calcium (340 nm/380 nm).[6] General procedure for cell viability. For cytotoxicity analysis, Jurkat cells were seeded in 96-well plates in complete medium and treated with increasing doses of transtaganolide C (4) or thapsigargin (1) at the indicated concentrations (µM) for 24 hours. Samples were then diluted with 300 µL of PBS and incubated 1 minute at 23 °C in the presence of propidium iodine (10 µg/ml). After incubation, cells were immediately analyzed by flow cytometry. The results are represented as the percentage of viability considering 100% viability for the untreated cells.[6] _____________________________________________________________________ [1] Methyl ester 30 was synthesized for GC studies using known methods:
Kapferer, T.; Brückner, R. Eur. J. Org. Chem. 2006, 2119–2133. [2] Iodo-cyclohexene (28) synthesized for GC studies using known methods:
Kropp, P. J.; McNeely, S. A.; Davis, R. D. J. Am. Chem. Soc. 1983, 105, 6907–6915.
[3] Appendino, G.; Prosperini, S.; Valdivia, C.; Ballero, M.; Colombano, G.; Billington, R. A.; Genazzani, A. A.; Sterner, O. J. Nat. Prod. 2005, 68, 1213–1217.
[4] Saouf, A.; Guerra, F. M.; Rubal, J. J.; Moereno-Dorado, F. J.; Akssira, M.; Mellouki, F.; López, M.; Pujadas, A. J.; Jorge, Z. D.; Massanet, G. M. Org Lett. 2005, 7, 881–884.
[5] Navarrete, C.; Sancho, R.; Caballero, F. J.; Pollastro, F.; Fiebich, B. L.; Sterner, O.; Appendino, G.; Muñoz, E. J. Pharmacol. Exp. Ther. 2006, 319, 422–430.
[6] Muñoz, E. Departamento de Biología Celular, Fisiología e Inmunología, Facultad de Medicina, Universidad de Cordoba, Cordoba, Spain. Personal communication, July 2013.
V. Spectra
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Figure SI-4C 13C NMR (75 MHz, CDCl3) of compound 17.
Figure SI-4B infrared spectrum (Thin Film, NaCl) of compound 17.
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Figure SI-5C 13C NMR (75 MHz, CDCl3) of compound 18.
Figure SI-5B infrared spectrum (Thin Film, NaCl) of compound 18.
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d SI-1
.
![Page 18: The Total Syntheses of Basiliolide C, epi-Basiliolide C, and ...authors.library.caltech.edu/50396/7/jo501924u_si_001.pdfS1 The Total Syntheses of Basiliolide C, epi-Basiliolide C,](https://reader036.fdocuments.net/reader036/viewer/2022071409/610386434560163fcf6084b9/html5/thumbnails/18.jpg)
S18
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Figure SI-6C 13C NMR (75 MHz, CDCl3) of compound SI-1.
Figure SI-6B infrared spectrum (Thin Film, NaCl) of compound SI-1.
![Page 19: The Total Syntheses of Basiliolide C, epi-Basiliolide C, and ...authors.library.caltech.edu/50396/7/jo501924u_si_001.pdfS1 The Total Syntheses of Basiliolide C, epi-Basiliolide C,](https://reader036.fdocuments.net/reader036/viewer/2022071409/610386434560163fcf6084b9/html5/thumbnails/19.jpg)
S19
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re S
I-7A
1 H N
MR
300
MH
z, C
DC
l 3) o
f com
poun
d 19
.
![Page 20: The Total Syntheses of Basiliolide C, epi-Basiliolide C, and ...authors.library.caltech.edu/50396/7/jo501924u_si_001.pdfS1 The Total Syntheses of Basiliolide C, epi-Basiliolide C,](https://reader036.fdocuments.net/reader036/viewer/2022071409/610386434560163fcf6084b9/html5/thumbnails/20.jpg)
S20
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Figure SI-7C 13C NMR (75 MHz, CDCl3) of compound 19.
Figure SI-7B infrared spectrum (Thin Film, NaCl) of compound 19.
![Page 21: The Total Syntheses of Basiliolide C, epi-Basiliolide C, and ...authors.library.caltech.edu/50396/7/jo501924u_si_001.pdfS1 The Total Syntheses of Basiliolide C, epi-Basiliolide C,](https://reader036.fdocuments.net/reader036/viewer/2022071409/610386434560163fcf6084b9/html5/thumbnails/21.jpg)
S21
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re S
I-8A
1 H N
MR
300
MH
z, C
DC
l 3) o
f com
poun
d 14
.
![Page 22: The Total Syntheses of Basiliolide C, epi-Basiliolide C, and ...authors.library.caltech.edu/50396/7/jo501924u_si_001.pdfS1 The Total Syntheses of Basiliolide C, epi-Basiliolide C,](https://reader036.fdocuments.net/reader036/viewer/2022071409/610386434560163fcf6084b9/html5/thumbnails/22.jpg)
S22
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Figure SI-8C 13C NMR (75 MHz, CDCl3) of compound 14.
Figure SI-8B infrared spectrum (Thin Film, NaCl) of compound 14.
![Page 23: The Total Syntheses of Basiliolide C, epi-Basiliolide C, and ...authors.library.caltech.edu/50396/7/jo501924u_si_001.pdfS1 The Total Syntheses of Basiliolide C, epi-Basiliolide C,](https://reader036.fdocuments.net/reader036/viewer/2022071409/610386434560163fcf6084b9/html5/thumbnails/23.jpg)
S23
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re S
I-9A
1 H N
MR
300
MH
z, C
DC
l 3) o
f com
poun
ds 21
and 22
.
![Page 24: The Total Syntheses of Basiliolide C, epi-Basiliolide C, and ...authors.library.caltech.edu/50396/7/jo501924u_si_001.pdfS1 The Total Syntheses of Basiliolide C, epi-Basiliolide C,](https://reader036.fdocuments.net/reader036/viewer/2022071409/610386434560163fcf6084b9/html5/thumbnails/24.jpg)
S24
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Figure SI-9C 13C NMR (75 MHz, CDCl3) of compounds 21 and 22.
Figure SI-9B infrared spectrum (Thin Film, NaCl) of compounds 21 and 22.
![Page 25: The Total Syntheses of Basiliolide C, epi-Basiliolide C, and ...authors.library.caltech.edu/50396/7/jo501924u_si_001.pdfS1 The Total Syntheses of Basiliolide C, epi-Basiliolide C,](https://reader036.fdocuments.net/reader036/viewer/2022071409/610386434560163fcf6084b9/html5/thumbnails/25.jpg)
S25
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re S
I-10A
1 H N
MR
300
MH
z, C
DC
l 3) o
f com
poun
ds 23
and 24
.
![Page 26: The Total Syntheses of Basiliolide C, epi-Basiliolide C, and ...authors.library.caltech.edu/50396/7/jo501924u_si_001.pdfS1 The Total Syntheses of Basiliolide C, epi-Basiliolide C,](https://reader036.fdocuments.net/reader036/viewer/2022071409/610386434560163fcf6084b9/html5/thumbnails/26.jpg)
S26
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Figure SI-10C 13C NMR (75 MHz, CDCl3) of compounds 23 and 24.
Figure SI-10B infrared spectrum (Thin Film, NaCl) of compounds 23 and 24.
![Page 27: The Total Syntheses of Basiliolide C, epi-Basiliolide C, and ...authors.library.caltech.edu/50396/7/jo501924u_si_001.pdfS1 The Total Syntheses of Basiliolide C, epi-Basiliolide C,](https://reader036.fdocuments.net/reader036/viewer/2022071409/610386434560163fcf6084b9/html5/thumbnails/27.jpg)
S27
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re S
I-11A
1 H N
MR
(500
MH
z, C
DC
l 3) o
f bas
iliol
ide
C (8
).
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AcO
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S28
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Figure SI-11C 13C NMR (125 MHz, CDCl3) of basiliolide C (8).
Figure SI-11B infrared spectrum (Thin Film, NaCl) of basiliolide C (8).
![Page 29: The Total Syntheses of Basiliolide C, epi-Basiliolide C, and ...authors.library.caltech.edu/50396/7/jo501924u_si_001.pdfS1 The Total Syntheses of Basiliolide C, epi-Basiliolide C,](https://reader036.fdocuments.net/reader036/viewer/2022071409/610386434560163fcf6084b9/html5/thumbnails/29.jpg)
S29
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re S
I-12A
1 H N
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(500
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z, C
DC
l 3) o
f epi
-bas
iliol
ide
C (9
).
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S30
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Figure SI-12C 13C NMR (125 MHz, CDCl3) of epi-basiliolide C (9).
Figure SI-12B infrared spectrum (Thin Film, NaCl) of epi-basiliolide C (9).
![Page 31: The Total Syntheses of Basiliolide C, epi-Basiliolide C, and ...authors.library.caltech.edu/50396/7/jo501924u_si_001.pdfS1 The Total Syntheses of Basiliolide C, epi-Basiliolide C,](https://reader036.fdocuments.net/reader036/viewer/2022071409/610386434560163fcf6084b9/html5/thumbnails/31.jpg)
S31
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re S
I-13A
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500
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.
![Page 32: The Total Syntheses of Basiliolide C, epi-Basiliolide C, and ...authors.library.caltech.edu/50396/7/jo501924u_si_001.pdfS1 The Total Syntheses of Basiliolide C, epi-Basiliolide C,](https://reader036.fdocuments.net/reader036/viewer/2022071409/610386434560163fcf6084b9/html5/thumbnails/32.jpg)
S32
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Figure SI-13C 13C NMR (125 MHz, CDCl3) of compound 11.
Figure SI-13B infrared spectrum (Thin Film, NaCl) of compound 11.
![Page 33: The Total Syntheses of Basiliolide C, epi-Basiliolide C, and ...authors.library.caltech.edu/50396/7/jo501924u_si_001.pdfS1 The Total Syntheses of Basiliolide C, epi-Basiliolide C,](https://reader036.fdocuments.net/reader036/viewer/2022071409/610386434560163fcf6084b9/html5/thumbnails/33.jpg)
S33
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re S
I-14A
1 H N
MR
300
MH
z, C
DC
l 3) o
f bas
iliop
yron
e (10)
.
![Page 34: The Total Syntheses of Basiliolide C, epi-Basiliolide C, and ...authors.library.caltech.edu/50396/7/jo501924u_si_001.pdfS1 The Total Syntheses of Basiliolide C, epi-Basiliolide C,](https://reader036.fdocuments.net/reader036/viewer/2022071409/610386434560163fcf6084b9/html5/thumbnails/34.jpg)
S34
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Figure SI-14C 13C NMR (125 MHz, CDCl3) of basiliopyrone (10).
Figure SI-14B infrared spectrum (Thin Film, NaCl) of basiliopyrone (10).
![Page 35: The Total Syntheses of Basiliolide C, epi-Basiliolide C, and ...authors.library.caltech.edu/50396/7/jo501924u_si_001.pdfS1 The Total Syntheses of Basiliolide C, epi-Basiliolide C,](https://reader036.fdocuments.net/reader036/viewer/2022071409/610386434560163fcf6084b9/html5/thumbnails/35.jpg)
S35
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re S
I-15A
1 H N
MR
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MH
z, C
DC
l 3) o
f tra
nsta
gano
lide
C (4
).
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MeO
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S36
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Figure SI-15C 13C NMR (125 MHz, CDCl3) of transtaganolide C (4).
Figure SI-15B infrared spectrum (Thin Film, NaCl) of transtaganolide C (4).
![Page 37: The Total Syntheses of Basiliolide C, epi-Basiliolide C, and ...authors.library.caltech.edu/50396/7/jo501924u_si_001.pdfS1 The Total Syntheses of Basiliolide C, epi-Basiliolide C,](https://reader036.fdocuments.net/reader036/viewer/2022071409/610386434560163fcf6084b9/html5/thumbnails/37.jpg)
S37
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re S
I-16A
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DC
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f tra
nsta
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D (5
).
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S38
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Figure SI-16C 13C NMR (125 MHz, CDCl3) of transtaganolide D (5).
Figure SI-16B infrared spectrum (Thin Film, NaCl) of transtaganolide D (5).