G. Raju et al. / Tetrahedron Letters 55 (2014) 6655–6657
6657
H
5
H
8
O
H
H
OH
10
O
7
6
1
2
9
4
3
11
1
(a)
(b)
Figure 2. (a) NOESY spectrum (in CDCl3) of 1 (b) energy minimized structure of 1.
10. Spectral data of some selected compounds. tert-Butyl((R)-3-((R)-oxiran-2-
6
6
7
7
O
O
yl)butoxy)diphenylsilane (7):
[a
]
D
+15.2 (c 0.55, MeOH); 1H NMR (CDCl3,
25
O
OH
10
O
O
4
4
1
2
1
2
300 MHz): d 7.71–7.64 (m, 4H), 7.46–7.34 (m, 6H), 3.77 (t, J = 6.0 Hz, 2H), 2.77–
2.64 (m, 2H), 2.47 (m, 1H), 1.85 (m, 1H), 1.66–1.43(m, 2H), 1.05 (s, 9H), 0.90 (d,
J = 6.0 Hz, 3H); 13C NMR (75 MHz, CDCl3): d 135.5, 133.9, 129.5, 127.5, 61.7,
8
9
8
9
5
11
5
11
3
3
10
2
1
56.7, 45.5, 36.9, 32.6, 26.8, 19.1, 15.4. HRMS calcd for
C22H30O2Na
H
HMBC
C
(M+Na)+ 377.1907, found 377.1906. (S)-1-((Hept-1-yn-4-yloxy)methyl)-4-
25
methoxybenzene (9): [
a
]
À12.4 (c 0.50, MeOH); 1H NMR (CDCl3, 500 MHz):
D
Figure 3. Key 2D NMR (HMBC) correlations of compounds 1 and 2.
d 7.27 (d, J = 8.5 Hz, 2H), 6.87 (d, J = 8.5 Hz, 2H), 4.58 (d, J = 11.2 Hz, 1H), 4.43
(d, J = 11.2 Hz, 1H), 3.78 (s, 3H), 3.52 (m, 1H), 2.48–2.35 (m, 2H), 2.00 (t,
J = 2.7 Hz, 1H), 1.64–1.57 (m, 2H), 1.51–1.29 (m, 2H), 0.90 (t, J = 7.3 Hz, 3H); 13
C
NMR (125 MHz, CDCl3): d 130.5, 129.2, 113.6, 81.3, 76.4, 70.9, 69.7, 55.1, 36.1,
23.7, 18.5, 13.9. HRMS calcd for
15H20O2Na (M+Na)+ 255.1355, found
255.1356. (3R,4S,9S)-1-(tert-Butyldiphenylsilyloxy)-9-(4-methoxybenzyloxy)-3-
In summary, we have reported the first total synthesis
of (6Z,9S)-3,4-trans-9-hydroxy-3-methyldodec-cis-6-en-4-olide 1
and (6Z)-3,4-trans-9-oxo-3-methyldodec-cis-6-en-4-olide 2 using
Ohira–Bestmann reaction, regioselective alkyne addition to termi-
nal carbon atom of epoxide, intramolecular TEMPO/BAIB mediated
oxidative lactonization, and Lindlar’s hydrogenation as the key
steps.
C
25
methyldodec-6-yn-4-ol (10):
[a
]
D
+21.0 (c 0.20, MeOH); 1H NMR (CDCl3,
500 MHz): d 7.72–7.63(m, 4H), 7.45–7.34 (m, 6H), 7.27 (d, J = 7.6 Hz, 2H), 6.86
(d, J = 8.6 Hz, 2H), 4.56 (d, J = = 11.2 Hz, 1H), 4.42 (d, J = 11.2 Hz, 1H), 3.79 (s,
3H), 3.74 (m, 1H), 3.67 (m, 1H), 3.56–3.45 (m, 2H), 2.67 (br. S, 1H), 2.47–2.30
(m, 4H), 1.88 (m, 1H), 1.78 (m, 1H), 1.58 (m, 2H), 1.51–1.41 (m, 2H), 1.34 (m,
1H), 1.04 (s, 9H), 0.90–0.85 (m, 6H); 13C NMR (125 MHz, CDCl3): d 159.0, 135.5,
133.5, 130.6, 129.6, 129.2, 127.6, 113.7, 79.4, 78.2, 74.0, 70.8, 62.0, 55.2, 36.2,
34.9, 34.7. 26.7, 24.9, 24.0, 19.1, 18.5, 15.9, 14.1. HRMS calcd for C37H50O4NaSi
(M+Na)+ 609.3370, found 609.3366. (3R,4S,9S)-9-(4-Methoxybenzyloxy)-3-
Acknowledgements
25
methyldodec-6-yne-1,4-diol (11): [
a
]
+6.6 (c 0.30, MeOH); 1H NMR (CDCl3,
D
300 MHz): d 7.27 (d, J = 8.6 Hz, 2H), 6.87 (d, J = 8.6 Hz, 2H), 4.56 (d, J = 11.3 Hz,
1H), 4.43, (d, J = 11.3 Hz, 1H), 3.80 (s, 3H), 3.72 (m, 1H), 3.62 (m, 1H), 3.54–3.43
(m, 2H), 2.77 (br s, 1H), 2.51–2.28 (m, 4H),1.86–1.17 (m, 7H), 0.96–0.84 (m,
6H). 13C NMR (125 MHz, CDCl3): d 159.1, 134.7, 130.4, 129.3, 127.6, 113.7, 79.6,
78.0, 74.0, 70.7, 60.5, 55.2, 36.1, 35.8, 35.7, 29.6, 26.5, 25.5, 23.8, 18.6, 16.7,
14.0. HRMS calcd for C21H32O4Na (M+Na)+ 371.2192, found 371.2193. (4R,5S)-
The authors (G.R. and N.R.) thank CSIR, New Delhi, India for the
financial support in the form of fellowships. All the authors thank
CSIR, New Delhi for financial support as part of XII Five Year plan
program under title TREAT (BSC-0116).
5-((S)-5-(4-Methoxybenzyloxy)oct-2-ynyl)-4-methyldihydrofuran-2(3H)-one
25
(12):
[
a
]
D
+10.0 (c 0.30, MeOH); 1H NMR (CDCl3, 300 MHz):
d 7.27 (d,
Supplementary data
J = 8.4 Hz, 2H), 6.87 (d, J = 8.4 Hz, 2H), 4.55 (d, J = 11.3 Hz, 1H), 4.42 (d,
J = 11.3 Hz, 1H), 4.13 (q, J = 5.6 Hz, 1H), 3.81(s, 3H), 3.48 (m, 1H), 2.76 (dd,
J = 17.5, 8.6 Hz, 1H), 2.64–2.56 (m, 2H), 2.54–2.35 (m, 2H), 2.18 (dd, J = 17.3,
8.1 Hz, 1H), 1.72–1.23 (m, 4H), 1.18 (d, J = 6.6 Hz, 3H), 0.90 (t, J = 7.3 Hz, 3H);
13C NMR (125 MHz, CDCl3): d 176.0, 159.0, 130.6, 129.2, 113.6, 84.4, 80.1,
75.4, 70.7, 55.2, 36.7, 36.1, 34.6, 29.6, 24.1, 23.9, 14.0. HRMS calcd for
Supplementary data associated with this article can be found,
C
21H32O4Na (M+Na)+ 362.2352, found 362.2332. (4R,5S)-5-((S,Z)-5-(4-
25
Methoxybenzyloxy)oct-2-enyl)-4-methyldihydrofuran-2(3H)-one
(13):
[a]
References and notes
D
+150.0 (c 0.10, MeOH); 1H NMR (CDCl3, 300 MHz): d 7.26 (d, J = 8.4 Hz, 2H),
6.87 (d, J = 8.4 Hz, 2H), 5.70–5.45 (m, 2H), 4.52–4.39 (m, 2H), 4.05 (q, J = 6.2 Hz,
1H), 3.80 (s, 3H), 3.43 (m, 1H), 2.65 (dd, J = 16.6,7.5 Hz, 1H), 2.55–2.15 (m, 5H),
1.57–1.20 (m, 5H), 1.11 (d, J = 6.4 Hz, 3H), 0.90 (t, J = 6.4 Hz, 3H); 13C NMR
(125 MHz, CDCl3): d 176.3, 159.0, 130.9, 129.5, 129.2, 124.6, 113.6, 86.5, 78.0,
70.7, 55.2, 36.9, 36.2, 35.1, 31.9, 31.4, 29.6, 18.6, 17.6, 14.1. HRMS calcd for
C
21H30O4Na (M+Na)+ 369.2036, found 369.2034. (6Z,9S)-3,4-trans-9-hydroxy-3-
À29.4 (c 0.55, MeOH); 1H NMR (CDCl3,
25
methyl dodec-cis-6-en-4-olide (1): [
300 MHz):
a
]
D
d
5.70–5.55 (m, 2H), 4.08 (m, 1H), 3.67 (m, 1H), 2.69 (dd,
J = 16.6,7.5 Hz, 1H), 2.58–2.42 (m, 2H), 2.33–2.14 (m, 4H), 1.53–1.39 (m, 3H),
1.38–1.23 (m, 1H),1.15 (d, J = 6.9 Hz, 3H), 0.93 (t, J = 6.9 Hz, 3H); 13C NMR
(75 MHz, CDCl3): d 176.1, 129.3, 126.1, 86.5, 71.0, 39.1, 37.0, 35.4, 35.3, 31.4,
18.8, 17.5, 14.0. HRMS calcd for
249.1458. (6Z)-3,4-trans-9-oxo-3-methyl
25 = +60.8 (c 0.2, MeOH); 1H NMR (CDCl3, 300 MHz): d 5.77 (m, 1H), 5.65
(m, 1H), 4.08 (m, 1H), 3.19 (d, J = 7.1 Hz, 2H), 2.68 (dd, J = 16.9, 7.7 Hz, 1H),
2.50–2.37 (m, 4H), 2.26 (m, 1H), 2.18 (m, 1H), 1.70–1.52 (m, 2H), 1.15 (d,
J = 6.4 Hz, 3H), 0.92 (t, J = 7.3 Hz, 3H) 13C NMR (125 MHz, CDCl3): d 208.2,
176.1, 126.6, 124.8, 86.1, 44.4, 41.5, 36.9, 35.2, 31.5, 17.4, 17.1, 13.6. HRMS
calcd for C13H21O3 (M+H)+ 225.1485, found 225.1481.
C
13H22O3Na (M+Na)+ 249.1461, found
dodec-cis-6-en-4-olide
(2):
[a]
D
11. As suggested by referee, HSQC, HMBC and NOESY experiments were conducted
for the thorough analysis of the structures of synthetic compounds 1 and 2. All
the data is incorporated as Supporting information.