P. Brémond et al. / Tetrahedron Letters 50 (2009) 5723–5725
5725
2. Asakawa, Y. Curr. Pharm. Des. 2008, 14, 3067–3088.
J = 11.2, 4.1 Hz, 1H), 5.11 (br d, J = 10.8 Hz, 1H), 5.23 (br d, J = 17.4 Hz, 1H), 5.51
(t, J = 8.3 Hz, 1H), 6.92 (ddd, J = 17.4, 10.8, 0.7 Hz, 1H). 13C NMR (75 MHz,
CDCl3): d 12.7, 15.5, 20.4, 24.2, 30.1, 30.8, 33.9, 36.0, 42.7, 74.1, 114.1, 127.0,
133.8, 134.4. HRMS (ESI) calcd for C14H25ONa: 231.1719 (M+Na+); found
3. (a) Takeda, R.; Mori, R.; Hirose, Y. Chem. Lett. 1982, 1625–1628; (b) Takeda, R.;
Naoki, H.; Iwashita, T.; Mizukawa, K.; Hirose, Y.; Isida, T.; Inoue, M. Bull. Chem.
Soc. Jpn. 1983, 56, 1125–1132.
4. (a) Audran, G.; Galano, J.-M.; Monti, H. Eur. J. Org. Chem. 2001, 2293–2296; (b)
Uttaro, J.-P.; Audran, G.; Palombo, E.; Monti, H. J. Org. Chem. 2003, 68, 5407–
5410; (c) Palombo, E.; Audran, G.; Monti, H. Tetrahedron Lett. 2003, 44, 6463–
6464; (d) Palombo, E.; Audran, G.; Monti, H. Synlett 2005, 2104–2106; (e)
Palombo, E.; Audran, G.; Monti, H. Tetrahedron 2005, 61, 9545–9549.
5. Aubin, Y.; Audran, G.; Monti, H. Tetrahedron Lett. 2006, 47, 3669–3671.
6. Silyl enol ether (+)-5 was synthesized from commercially available (R)-
Pulegone (+)-4 according to the literature: (a) Formation of an enantiopure
cis/trans mixture of 2,3-dimethylcyclohexanone: methylation see Tori, M.;
Uchida, N.; Sumida, A.; Furuta, H.; Asakawa, Y. J. Chem. Soc., Perkin Trans. 1
1995, 1513–1517 and acid-induced retro aldolisation see Dagneau, P.; Canonne
P. Tetrahedron: Asymmetry 1996, 7, 2817–2820; (b) Formation of silyl enol ether
(+)-5: Taishi, T.; Takechi, S.; Mori, S. Tetrahedron Lett. 1998, 39, 4347–4350.
1- LDA
231.1721. Compound (ꢀ)-7b. ½a D25
ꢁ
ꢀ21.8 (c 1.0, CHCl3), 1H NMR (300 MHz,
CDCl3): d 0.81 (s, 3H), 0.84 (d, J = 6.7 Hz, 3H), 1.18–1.30 (m, 1H), 1.38–1.47 (m,
2H), 1.51–1.57 (m, 2H), 1.59–1.63 (m, 1H), 1.64–1.67 (m, 1H), 1.74–1.81 (m,
1H), 1.85 (br q, J = 1.1 Hz, 3H), 2.22 (dd, J = 15.0, 7.8 Hz, 1H), 2.30 (dd, J = 15.0,
8.5 Hz, 1H), 3.57 (br s, 1H), 5.11 (br d, J = 10.8 Hz, 1H), 5.23 (br d, J = 17.3 Hz,
1H), 5.55 (br t, J = 8.3 Hz, 1H), 6.87 (ddd, J = 17.3, 10.8, 0.9 Hz, 1H). 13C NMR
(75 MHz, CDCl3): d 15.8, 17.1, 20.1, 20.4, 29.0, 30.4, 34.4, 35.2, 40.9, 73.0, 114.2,
127.6, 133.6, 134.0. HRMS (ESI) calcd for C14H24ONa: 231.1719 (M+Na+); found
231.1717. Compound (+)-9. ½a D25
ꢁ
+4.9 (c 1.0, CHCl3), 1H NMR (300 MHz, CDCl3):
d 0.88 (d, J = 6.7 Hz, 3H), 0.99 (s, 3H), 1.48–1.96 (partially overlapped m, 5H),
1.79 (br q, J = 1.1 Hz, 3H), 2.28–2.45 (m, 3H), 2.53 (ddd, J = 14.9, 6.6, 1.0 Hz, 1H),
5.08 (br d, J = 10.8 Hz, 1H), 5.19 (br d, J = 17.3 Hz, 1H), 5.27 (br t, J = 7.4 Hz, 1H),
6.78 (ddd, J = 17.3, 10.8, 0.7 Hz, 1H). 13C NMR (75 MHz, CDCl3): d 15.7, 19.1,
20.2, 24.2, 29.2, 33.9, 38.5, 38.7, 52.6, 113.9, 126.9, 133.7, 133.9, 215.8. HRMS
(ESI) calc for C14H23O: 207.1743 [M+H+]; found: 207.1737. (+)-Striatene (+)-1.
O
O
OTMS
NaI, TMSCl
then MeI
2 - HCl
62%
R
½ ꢁ
a 2D5 + 60.3 (c 1.0, CHCl3), 1H NMR (300 MHz, CDCl3): d 0.84 (d, J = 6.8 Hz, 3H),
HMDS
90%
0.90 (s, 3H), 1.39–1.47 (m, 2H), 1.61–1.70 (partially overlapped m, 1H), 1.63 (br
q, J = 1.4 Hz, 3H), 1.82 (br s, 3H), 1.94–2.01 (m, 2H), 2.17 (br dd, J = 15.9, 5.0 Hz,
1H), 2.42 (dd, J = 15.9, 8.9 Hz, 1H), 5.08 (d, J = 10.8 Hz, 1H), 5.16–5.22 (partially
overlapped m, 1H), 5.19 (d, J = 17.4 Hz, 1H), 5.46 (br s, 1H), 6.80 (dd, J = 17.4,
10.8 Hz, 1H). 13C NMR (75 MHz, CDCl3): d 16.2, 19.4, 20.2, 20.8, 25.5, 27.2, 34.3,
34.3, 40.9, 113.4, 124.6, 128.4, 133.3, 134.2, 139.4. HRMS (ESI) calcd for
C15H24Ag: 311.0923 [M+Ag+]; found: 311.0922.
(+)-5
(+)-4
mixture of cis/trans
2,3-dimethylcyclohexanone
diastereoisomers
(R)-Pulegone
7. Proszenyák, A.; Brꢀndvang, M.; Charnock, C.; Gundersen, L.-L. Tetrahedron
2009, 65, 194–199.
11. (a) Hart, D. W.; Blackburn, T. F.; Schwartz, J. J. Am. Chem. Soc. 1975, 97, 679–
680; For a convenient procedure of hydrozirconation, see: (b) Huang, Z.;
Negishi, E. Org. Lett. 2006, 8, 3675–3678.
12. Details of the X-ray structure for compound (+)-8 can be obtained from the
Cambridge Crystallographic Data Centre: CCDC 736783. Copies of the data can
be obtained free of charge on application to CCDC, 12 Union Road, Cambridge
CB2 1EZ, UK [Fax: (internat.) +44-1223-336-033; E-mail: deposit@ccdc.cam.
ac.uk]. C21H26N2O6, M = 402.44 g molꢀ1. The colourless single crystal (crystal
size/mm3: 0.3 ꢂ 0.15 ꢂ 0.10) was analyzed at 293 K with a Bruker Nonius
8. (a) Shing, T. K. M.; Zhu, X. Y.; Yeung, Y. Y. Chem. Eur. J. 2003, 9, 5489–5500;
(b) Wu, Z.; Wouters, J.; Poulter, C. D. J. Am. Chem. Soc. 2005, 127, 17433–17438.
9. Rearrangement of commercially available 3-methyl-1-penten-4-yn-3-ol under
acidic conditions as described in the literature (Cymerman, J.; Heilbron, I. M.;
Jones, E. R. H. J. Chem. Soc. 1945, 90–94) afforded
a Z/E mixture of 3-
methylpent-4-en-1-yn-3-ol in favour of the Z-stereoisomer (85:15 by GC). The
major Z-stereoisomer was easily isolated in pure form by fractional distillation
of the mixture through a spinning band.
10. All new compounds were fully characterized spectroscopically. Representative
spectra data for some new compounds: Compound (+)-6a. ½a D25
ꢁ
+82.5 (c 1.0,
Kappa-CCD
monochromated Mo-K
space group P-32,
automated
four-circle
radiation (k = 0.71073 Å). Crystal data: trigonal,
a = 15.888(5) Å, b = 15.888(5) Å, c = 7.307(5) Å,
(Mo-
diffractometer
using
graphite
CHCl3), 1H NMR (300 MHz, CDCl3): d 0.93 (d, J = 7.7 Hz, 3H), 1.00 (s, 3H), 1.47–
1.71 (m, 2H), 1.82 (br q, J = 1.5 Hz, 3H), 1.74–1.98 (partially overlapped m, 3H),
2.26–2.44 (m, 2H), 2.45–2.61 (m, 2H), 3.08 (s, 1H), 5.69 (br t, J = 8.0 Hz, 1H). 13C
NMR (75 MHz, CDCl3): d 15.8, 18.8, 23.2, 24.5, 29.4, 37.3, 38.5, 39.2, 52.5, 80.8,
83.4, 118.7, 136.1, 215.8. HRMS (ESI) calcd for C14H21O: 205.1587 (M+H+);
a
V = 1597.4(13) Å3, Z = 3, Dx = 1.255 g/cm3, F(0 0 0) = 642, and
l
K ) = 0.92 cmꢀ1. 265 parameters were refined on F2 using 1806 reflections to
a
2
final indices R1 [F2 >4
r
(F2)] = 0.0559, wR2½ðw ¼ 1=½r2ðF2oÞ þ ð0:0535PÞ þ
0:3592P) where P ¼ ðF2o þ 2Fc2Þ=3ꢁ ¼ 0:1193. Residual Fourier/e Åꢀ3:ꢀ0.196;
found 205.1578. Compound (+)-6b. ½a D25
ꢁ
+72.0 (c 1.0, CHCl3), 1H NMR (300 MHz,
0.162.
CDCl3): d 0.99 (d, J = 7.7 Hz, 3H), 1.09 (s, 3H), 1.62–1.73 (m, 2H), 1.81 (br s, 3H),
1.75–1.84 (partially overlapped m, 1H), 2.24–2.33 (m, 3H), 2.48–2.58 (m, 2H),
2.79 (dd, J = 14.8, 7.5 Hz, 1H), 3.12 (s, 1H), 5.52 (br t, J = 7.0 Hz, 1H). 13C NMR
(75 MHz, CDCl3): d 15.9, 20.2, 23.2, 25.8, 29.6, 33.4, 38.7, 43.4, 52.7, 81.3, 83.1,
119.6, 134.3, 215.7. HRMS (ESI) calcd for C14H21O: 205.1587 (M+H+); found
13. Griffith, W. P.; Ley, S. V. Aldrichim. Acta 1990, 23, 13–19.
14. Comins, D. L.; Dehghani, A.; Foti, C. J.; Joseph, S. P. Org. Synth. 1977, 74, 77–83.
15. (a) Pérez, I.; Pérez Sestelo, J.; Sarandeses, L. A. Org. Lett. 1999, 1, 1267–1269; (b)
Pérez, I.; Pérez Sestelo, J.; Sarandeses, L. A. J. Am. Chem. Soc. 2001, 123, 4155–
4160.
16. (a) Marshall, J. A.; Zou, D. Tetrahedron Lett. 2000, 41, 1347–1350; Reviews: (b)
Neghishi, E.; Hu, Q.; Huang, Z.; Qian, M.; Wang, G. Aldrichim. Acta 2005, 38, 71–
92.
205.1577. Compound (ꢀ)-7a. Mp = 49 °C, ½a D25
ꢁ
ꢀ17.4 (c 1.0, CHCl3), 1H NMR
(300 MHz, CDCl3): d 0.80 (s, 3H), 0.85 (d, J = 6.7 Hz, 3H), 1.20–1.26 (m, 1H),
1.28–1.37 (m, 2H), 1.40–1.49 (m, 2H), 1.62–1.70 (m, 2H), 1.86 (br q, J = 1.0 Hz,
3H), 2.06 (dd, J = 14.9, 7.8 Hz, 1H), 2.52 (dd, J = 14.9, 8.7 Hz, 1H), 3.41 (dd,