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DOI: 10.1055/s-0029-1217737
An Expedient Total Synthesis of (-)-Cladospolide A
Publication History
Publication Date:
27 August 2009 (online)
Abstract
A simple and efficient total synthesis of (-)-cladospolide A is described here, which involves either olefin cross metathesis or Julia-Kocienski olefination and Yamaguchi macrolactonization as key steps.
Key words
olefin cross metathesis - Julia-Kocienski olefination - macrolactonization - cladospolides - total synthesis
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References and Notes
Spectral Data
for Selected Compounds
Compound 22: R
f
= 0.28
(2% EtOAc in hexane); [α]D
²0
-27.6
(c 0.50, CHCl3). IR (neat):
3020, 2931, 1657, 1216, 1045, 669 cm-¹. ¹H
NMR (400 MHz, CDCl3): δ = 5.45-5.42 (2
H, m), 4.09-4.05 (3 H, m), 3.80-3.74 (1 H, m),
3.66 (1 H, dd, J = 11.3,
4.8 Hz), 2.13-2.03 (4 H, m), 1.63-1.53 (2 H, m),
1.40 (3 H, s), 1.31 (3 H, s), 1.10 (3 H, d, J = 6.1
Hz), 0.90 (9 H, s), 0.88 (9 H, s), 0.86 (9 H, s), 0.11 (3 H, s),
0.08 (3 H, s), 0.06 (6 H, s), 0.04 (3 H, s), 0.03 (3 H, s). ¹³C
NMR (100 MHz, CDCl3): δ = 132.0,
127.2, 107.8, 77.4, 76.4, 72.6, 68.8, 65.3, 43.0, 30.1, 29.1, 28.4,
26.0, 25.96, 25.90, 23.3, 18.4, 18.1, -3.5, -4.5, -4.6, -4.7, -5.3, -5.4.
Compound 23: R
f
= 0.26
(2% EtOAc in hexanes); [α]D
²0
-29.7
(c 0.66, CHCl3). IR (neat):
3021, 2930, 2858, 2640, 1380, 1216, 1044, 669 cm-¹. ¹H
NMR (400 MHz, CDCl3): δ = 4.08-4.04
(2 H, m), 3.79-3.73 (3 H, m), 3.68-3.64 (1 H, m),
1.65-1.24 (10 H, complex m), 1.39 (3 H, s), 1.30 (3 H, s),
1.09 (3 H, d, J = 6.1
Hz), 0.90 (9 H, s), 0.87 (9 H, s), 0.85 (9 H, s), 0.10 (3 H, s),
0.07 (3 H, s), 0.05 (6 H, s), 0.037 (3 H, s), 0.033 (3 H, s). ¹³C
NMR (100 MHz, CDCl3): δ = 107.7,
76.6, 72.6, 68.5, 65.3, 39.6, 30.0, 29.8, 28.4, 26.1, 26.0, 25.96,
25.90, 23.8, 18.4, 18.2, 18.1, -3.5, -4.4, -4.7,
-4.8, -5.3, -5.4.
HRMS (EI): m/z calcd for [C32H70O5Si3 + Na]+ :
641.4429; found: 641.4412.
Compound 6: R
f
= 0.34
(10% EtOAc in hexanes); [α]D
²0
-12.7
(c 0.83, CHCl3). IR (neat):
3020, 2937, 2401, 1712, 1382, 1216, 1023, 669 cm-¹. ¹H
NMR (400 MHz, CDCl3): δ = 6.96
(1 H, dd, J = 15.7,
9.1 Hz), 6.05 (1 H, d, J = 15.8 Hz),
5.08-5.15 (1 H, m), 4.68 (1 H, dd, J = 8.8,
6.4 Hz), 4.10 (1 H, ddd, J = 7.9,
6.1, 1.8 Hz), 1.73-1.61 (2 H, m), 1.54-1.20 (7
H, m), 1.48 (3 H, s), 1.34 (3 H, s), 1.27 (3 H, d, J = 6.4
Hz), 0.98-0.92 (1 H, m). ¹³C
NMR (100 MHz, CDCl3): δ = 166.9,
145.1, 124.3, 109.4, 79.5, 76.4, 72.7, 33.3, 30.7, 28.1, 27.9, 25.4,
21.8, 20.0, 18.3.
(-)-Cladospolide A
(1): R
f
= 0.19
(50% EtOAc in hexanes); mp 90-92 ˚C; [α]D
²0 -40.4
(c 0.50, CHCl3). IR (KBr):
3437, 2927, 2870, 1713, 1651, 1462, 1377, 1269, 1165, 1021, 880 cm-¹. ¹H
NMR (400 MHz, CDCl3): δ = 6.80
(1 H, dd, J = 16.0,
5.5 Hz), 6.20 (1 H, dd, J = 16.0,
1.5 Hz), 5.15-5.08 (1 H, m), 4.55-4.53 (1 H, m),
3.65 (1 H, ddd, J = 9.1,
1.8, 1.2 Hz), 1.81-1.11 (9 H, complex m), 1.27 (3 H, d, J = 6.4 Hz), 0.90-0.84
(1 H, m). ¹³C NMR (100 MHz, CDCl3): δ = 167.9, 145.5,
122.2, 74.6, 72.9, 72.8, 32.3, 30.6, 28.1, 25.0, 22.5, 18.9.