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DOI: 10.1055/s-0029-1219931
Synthesis of the Tetrahydropyran Subunit (C8-C20 Fragment) of (-)-Dactylolide and (-)-Zampanolide
Publikationsverlauf
Publikationsdatum:
10. Mai 2010 (online)
Abstract
The asymmetric synthesis of the tetrahydropyran containing C8-C20 fragment, a common key subunit of both (-)-dactylolide and (-)-zampanolide, is described. The salient feature of this synthesis is the extension of carbon chains using alkynols followed by the use of an alkyne system to generate the desired functionalities, in particular formation of the embedded pyran via an intramolecular oxa-Michael addition of a β-hydroxyynone.
Key words
tetrahydropyran - dactylolide - zampanolide - hydroxyynone - alkyne
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- Supporting Information
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References and Notes
Spectral Data
for Representative Compounds
(
S
)-8-(Benzyloxy)-1-(
tert
-butyldiphenylsilyloxy)-2-hydroxyoct-5-yn-4-one
(8)
[α]D
³¹ -8.5
(c 1.0, CHCl3). IR (KBr): νmax = 3442,
2929, 2215, 1670, 1426, 1110, 822, 703 cm-¹. ¹H
NMR (400 MHz, CDCl3): δ = 7.65-7.59
(m, 4 H), 7.43-7.21 (m, 11 H), 4.53 (s, 2 H), 4.25-4.16
(m, 1 H), 3.60 (t, J = 2.9
Hz, 2 H), 3.60 (td, J = 10.9,
5.1 Hz, 2 H), 2.74-2.71 (m, 2 H), 2.65 (t, J = 6.5 Hz,
2 H), 2.03 (br s, 1 H), 1.06 (s, 9 H). ¹³C
NMR (75 MHz, CDCl3): δ = 186.0, 137.6,
135.4, 132.9, 129.8, 128.4, 127.7, 127.6, 91.6, 81.4, 73.0, 68.0,
67.0, 66.8, 48.7, 26.8, 20.4, 19.1. ESI-HRMS: m/z calcd
for C31H36NaO4Si: 523.2306 [M + Na]+;
found: 523.2295.
(2
S
,6
S
)-2-[2-(Benzyloxy)ethyl]-6-[(
tert
-butyldiphenyl-silyloxy)methyl]dihydro-2
H
-pyran-4 (3
H
)-one (10)
[α]D
²7 -10
(c 1.0, CHCl3). IR (KBr): νmax = 2928,
2858, 1640, 1463, 1426, 1363, 1111, 701 cm-¹. ¹H
NMR (300 MHz, CDCl3): δ = 7.64 (td, J = 7.5, 1.3
Hz, 4 H), 7.44-7.17 (m, 11 H), 4.46 (AB, J = 12.2
Hz 1 H), 4.41 (AB, J = 12.2 Hz,
1 H), 3.83-3.49 (m, 6 H), 2.35 (dd, J = 14.1,
4.5 Hz, 3 H), 2.20 (ddd, J = 14.1,
11.5, 4.5 Hz, 1 H), 1.95-1.73 (m, 2 H), 1.02 (s, 9 H). ¹³C
NMR (75 MHz, CDCl3): δ = 207.3, 135.6,
135.5, 133.3, 133.2, 129.6, 128.3, 127.6, 127.5, 77.0, 73.9, 73.0,
66.3, 66.0, 47.7, 44.0, 36.4, 26.7, 19.2. ESI-HRMS: m/z calcd for C31H38NaO4Si:
525.2437 [M + Na]+; found:
525.2443.
(
E
)-6-[(2
S
,6
S
)-6-Allyl-4-methylenetetrahydro-2
H
-pyran-2-yl]-5-methylhex-5-en-2-yn-1-ol
(16)
[α]D
²8 -15.3
(c 0.5, CHCl3). IR (KBr): νmax = 3458,
2932, 2853, 2325, 1647, 1427, 1219, 1015, 893, 771 cm-¹. ¹H NMR
(300 MHz, CDCl3): δ = 5.91-5.74
(m, 1 H), 5.48 (dq, J = 7.1,
1.1 Hz, 1 H), 5.12-5.08 (m, 1 H), 5.08-5.01 (m,
1 H), 4.71 (t, J = 1.5
Hz, 2 H), 4.26 (s, 2 H), 4.00 (ddd, J = 10.9,
7.9, 2.8 Hz, 1 H), 3.41-3.30 (m, 1 H), 2.93 (s, 2 H), 2.45-2.32
(m, 1 H), 2.29-2.12 (m, 3 H), 2.06 (t, J = 12.8
Hz, 1 H), 1.93 (t, J = 12.8
Hz, 1 H), 1.58 (br s, 1 H), 1.75 (s, 3 H). ¹³C
NMR (75 MHz, CDCl3): δ = 143.8, 134.0,
133.3, 126.4, 116.5, 108.3, 82.6, 80.4, 76.1, 75.1, 50.9, 40.2,
39.4, 29.2, 28.3, 16.4. ESI-HRMS: m/z calcd
for C16H22NaO2: 269.1512 [M + Na]+;
found: 269.151.
[(2
R
,3
R
)-3-{(
E
)-3-[(2
S
,6
S
)-6-Allyl-4-methylene-tetrahydro-2
H
-pyran-2-yl]-2-methylallyl}oxiran-2-yl]-methanol
(5)
[α]D
²7 -15.5
(c 1.0, CH2Cl2).
IR (KBr): νmax = 3425, 3074, 2980,
2937, 2896, 1649, 1433 cm-¹. ¹H
NMR (300 MHz, CDCl3): δ = 5.92-5.70
(m, 1 H), 5.34 (dq, J = 7.7,
1.0 Hz, 1 H), 5.14-5.10 (m, 1 H), 5.09-5.02 (m,
1 H), 4.74 (t, J = 1.5 Hz,
2 H), 4.04 (ddd, J = 10.8,
7.7, 2.6 Hz, 1 H), 3.98-3.88 (m, 1 H), 3.71-3.60
(m, 1 H), 3.43-3.32 (m, 1 H), 3.07 (ddd, J = 5.6,
5.6, 2.2 Hz, 1 H), 2.97-2.93 (m, 1 H), 2.41 (dd, J = 14.1,
6.2 Hz, 1 H), 2.33 (dd, J = 14.5,
6.0 Hz, 1 H), 2.28-2.14 (m, 4 H), 2.05 (t, J = 12.6 Hz,
1 H), 1.93 (t, J = 12.6
Hz, 1 H), 1.76 (d, J = 1.1
Hz, 3 H). ¹³C NMR (75 MHz, CDCl3): δ = 144.2,
135.0, 134.4, 128.0, 116.9, 108.7, 77.7, 75.4, 61.4, 58.2, 54.5,
41.5, 40.7, 40.6, 39.8, 17.3. ESI-HRMS: m/z calcd
for C16H24NaO3: 287.1618 [M + Na]+;
found: 287.1626.