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DOI: 10.1055/s-0029-1217707
Enantioselective Synthesis of the Lyngbouilloside Macrolactone Core
Publication History
Publication Date:
31 July 2009 (online)
Abstract
The macrocyclic core of the marine natural product lyngbouilloside has been prepared in a convergent and enantioselective manner.
Key words
lyngbouilloside - lactone - ring-closing metathesis - dithiane
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References and Notes
X-ray crystallographic data for compounds 9-11 have been deposited with the Cambridge Crystallographic Data Centre as CCDC733929, CCDC733930 and CCDC733931, respectively.
14Data for Compound 4: [α]D ²5 -10.6 (c 0.805, CHCl3). IR (neat): 2932, 1734, 1612, 1513, 1355, 1302, 1245, 1172, 1075, 1031 cm-¹. ¹H NMR (600 MHz, CDCl3): δ = 7.25 (2 H, d, J = 8.5 Hz), 6.89 (2 H, d, J = 8.6 Hz), 5.90 (1 H, ddd, J = 17.2, 10.5, 6.0 Hz), 5.37 (1 H, d, J = 17.2 Hz), 5.26 (1 H, d, J = 10.5 Hz), 4.66-4.63 (1 H, m, H7), 4.50 (2 H, s), 3.97-3.93 (1 H, m), 3.81 (3 H, s), 2.90 (1 H, dd, J = 17.3, 6.0 Hz), 2.58 (1 H, dd, J = 17.3, 7.9 Hz), 2.35 (dt, 1 H, J = 13.8, 3.4 Hz), 1.72 (1 H, ddd, J = 13.8, 11.8, 9.4 Hz). ¹³C NMR (150 MHz, CDCl3): δ = 169.8, 159.5, 135.3, 129.5, 129.3, 117.4, 114.0, 77.3, 70.1, 69.7, 55.3, 36.9, 35.3. ESI-HRMS: m/z calcd for C15H18O4Na [M + Na]+: 285.1103; found: 285.1094. Anal. Calcd for C15H18O4: C, 68.68; H, 6.92. Found: C, 68.64; H, 6.97.
19
Data for Compound
3
[α]D
²5 +26.5
(c 0.80, CHCl3). IR (neat):
2958, 2930, 2857, 1732, 1639, 1364, 1246, 1101, 1075, 1041 cm-¹. ¹H
NMR (600 MHz, CDCl3): δ = 7.35-7.33
(4 H, m), 7.29-7.27 (1 H, m), 5.74 (1 H, ddd, J = 17.3,
10.4, 6.8 Hz), 5.05-5.01 (2 H, m), 4.49 (2 H, s), 3.89-3.87
(1 H, m), 3.46-3.42 (2 H, m), 2.42-2.40 (1 H,
m), 2.08 (1 H, dd, J = 14.7,
3.7 Hz), 1.96-1.93 (1 H, m), 1.95 (3 H, s), 1.87-1.84
(1 H, m), 1.63-1.56 (3 H, m), 1.45 (3 H, s), 1.00 (3 H,
d, J = 6.9
Hz), 0.89 (9 H, s), 0.08 (3 H, s), 0.07 (3 H, s). ¹³C
NMR (150 MHz, CDCl3): δ = 170.2, 140.5,
138.5, 128.3, 127.7, 127.5, 114.9, 84.0, 73.0, 72.3, 70.6, 43.9,
41.0, 35.9, 26.0, 24.2, 24.2, 22.4, 18.1, 13.4, -4.0, -4.2.
ESI-HRMS: m/z calcd for C26H44O4SiNa [M + Na]+:
471.2907; found: 471.2907. Anal. Calcd for C26H44O4Si:
C, 65.59; H, 9.88. Found: C, 69.64; H, 9.85.
Data for Compound
24
[α]D
²5 -31.80
(c 0.47, CHCl3). IR (neat):
2930, 2856, 1727, 1614, 1514, 1247, 1077, 1038 cm-¹. ¹H
NMR (600 MHz, CDCl3): δ = 7.34-7.31
(4 H, m), 7.29-7.25 (1 H, m), 7.24 (2 H, d, J = 8.8 Hz),
6.85 (2 H, d, J = 8.8
Hz), 5.84 (1 H, ddd, J = 16.9,
10.5, 6.1 Hz), 5.75 (1 H, ddd, J = 17.3,
10.8, 6.8 Hz), 5.26 (1 H, d, J = 16.9
Hz), 5.12 (1 H, d, J = 10.5
Hz), 5.05-5.00 (2 H, m), 4.49 (1 H, d, J = 11.3
Hz), 4.48 (2 H, s), 4.44 (1 H, d, J = 11.3
Hz), 4.01 (1 H, dd, J = 11.3,
5.4 Hz), 3.91-3.85 (2 H, m), 3.79 (3 H, s), 3.47-3.41
(2 H, m), 3.20 (3 H, s), 2.74 (1 H, d, J = 13.6
Hz), 2.51 (1 H, d, J = 13.6 Hz),
2.48 (1 H, dd, J = 13.0,
3.8 Hz), 2.45-2.40 (1 H, m), 2.10 (1 H, dd, J = 14.8,
3.3 Hz), 2.07 (1 H, d, J = 12.8
Hz), 1.95 (2 H, t, J = 7.9
Hz), 1.70-1.55 (4 H, m), 1.49 (3 H, s), 1,33 (1 H, q, J = 11.9 Hz),
1.00 (2 H, d, J = 6.9
Hz), 0.90 (9 H, s), 0.08 (3 H, s), 0.08 (3 H, s). ¹³C
NMR (150 MHz, CDCl3): δ = 168.1, 159.1,
140.4, 138.6, 138.0, 130.8, 129.1, 128.3, 127.6, 127.5, 115.5, 114.9,
113.8, 99.7, 84.9, 72.9, 72.2, 71.2, 70.5, 70.1, 69.5, 55.3, 47.9,
43.9, 43.1, 41.0, 39.7, 37.2, 36.0, 26.0, 24.1 (2 × C),
18.1, 13.3, -3.9, -4.2. ESI-HRMS: m/z calcd for C42H64O8NaSi [M + Na]+:
747.4268; found: 747.4249. Anal. Calcd for C42H64O8Si:
C, 69.58; H, 8.90. Found: C, 69.53; H, 9.07.
Data for Compound
2
[α]D
²5 -68.3
(c 0.925, C6H6).
IR (neat): 2932, 2856, 1723, 1614, 1514, 1246, 1102, 1063 cm-¹. ¹H
NMR (600 MHz, CDCl3): δ = 7.36-7.32
(4 H, m), 7.29-7.24 (3 H, m), 6.87 (2 H, d, J = 8.1 Hz),
5.92 (1 H, dd, J = 15.9,
2.7 Hz), 5.64 (1 H, dd, J = 16.0,
9.6 Hz), 4.51-4.46 (3 H, br s), 4.45 (2 H, s), 3.95-3.90
(1 H, m), 3.80 (4 H, br s), 3.49-3.40 (2 H, m), 3.20 (3
H, s), 2.85 (1 H, br d, J = 16.5
Hz), 2.82 (1 H, d, J = 12.9 Hz),
2.42-2.37 (1 H, m), 2.31 (1 H, d, J = 12.9
Hz), 2.27-2.18 (4 H, m), 1.75 (1 H, d, J = 16.1
Hz), 1.74-1.62 (2 H, m), 1.50-1.39 (2 H, m), 1.31
(3 H, s), 0.95 (2 H, d, J = 7.0
Hz), 0.86 (9 H, s), 0.03 (3 H, s), 0.01 (3 H, s). ¹³C
NMR (150 MHz, CDCl3): δ = 168.8, 159.1,
138.5, 136.3, 134.4, 130.8, 129.0, 128.4, 127.7, 127.5, 113.8, 98.1,
85.8, 73.7, 73.0, 70.5, 69.7, 69.7, 69.2, 55.3, 47.7, 45.5, 44.1,
41.0, 37.4, 35.8, 32.7, 25.9, 24.3, 23.5, 18.0, 11.7, -3.8, -4.8.
ESI-HRMS:
m/z calcd
for C40H60O8NaSi [M + Na]+:
719.3955; found: 719.3945.
Data for Compound
26
[α]D
²5 -61
(c 0.235, CHCl3). IR (neat):
3464, 2924, 2853, 1721, 1613, 1514, 1455, 1246, 1098, 1041 cm-¹. ¹H
NMR (500 MHz, C6D6): δ = 7.33
(2 H, d, J = 7.8
Hz), 7.22 (2 H, d, J = 8.6
Hz), 7.19 (2 H, d, J = 7.5
Hz), 7.12-7.07 (1 H, m), 6.80 (2 H, d, J = 8.6
Hz), 6.04 (1 H, dd, J = 15.9,
3.5 Hz), 5.97 (1 H, ddd, J = 15.9,
8.2, 1.1 Hz), 4.36 (1 H, d, J = 11.6 Hz),
4.34-4.31 (4 H, m, H7), 4.01-3.96 (1 H, m), 3.74-3.70 (1
H, m), 3.35-3.27 (2 H, m), 3.29 (3 H, s), 3.02 (3 H, s),
2.88 (1 H, J = 12.2
Hz), 2.73 (1 H, br d, J = 16.1
Hz), 2.53 (1 H, dd, J = 13.5,
9.1 Hz), 2.54-2.46 (1 H, m), 2.31 (1 H, dd, J = 13.5,
7.1 Hz), 2.22-2.15 (1 H, m), 2.15 (1 H, d, J = 12.2 Hz),
2.14-2.08 (1 H, m), 1.75-1.66 (3 H, m), 1.63-1.54
(1 H, m), 1.47 (1 H, d, J = 16.1
Hz), 1.41 (3 H, s), 1.01 (3 H, d, J = 6.8
Hz). ¹³C NMR (125 MHz, C6D6): δ = 168.5,
159.7, 139.4, 136.9, 134.6, 131.4, 128.5, 128.3, 127.7, 127.5, 114.1,
98.9, 85.7, 73.0, 72.7, 70.7, 69.9, 69.9, 69.7, 54.7, 47.4, 45.0,
44.2, 39.8, 38.5, 36.1, 33.5, 24.8, 23.7, 11.9. ESI-HRMS: m/z
calcd for C34H46O8Na [M + Na]+:
605.3090; found: 605.3078.
We have conducted our own NMR analysis of a sample of natural lyngbouilloside kindly donated to us by Professor Gerwick.