K. Tomooka et al. / Tetrahedron Letters 49 (2008) 6327–6329
6329
4. For reviews, see: (a) Parsons, A. F. Tetrahedron 1996, 52, 4149–4174; (b)
Moloney, M. G. Nat. Prod. Rep. 2002, 19, 597–616; For recent syntheses, see: (c)
Morita, Y.; Tokuyama, H.; Fukuyama, T. Org. Lett. 2005, 7, 4337–4340; (d) Trost,
B. M.; Rudd, M. T. J. Am. Chem. Soc. 2005, 127, 4763–4776; (e) Hodgson, D. M.;
Hachisu, S.; Andrews, M. D. Org. Lett. 2005, 7, 815–817; (f) Poisson, J.-F.;
Orellana, A.; Greene, A. E. J. Org. Chem. 2005, 70, 10860–10863; (g) Martinez, M.
M.; Hoppe, D. Eur. J. Org. Chem. 2005, 1427–1443; (h) Anderson, J. C.;
O’Loughlin, J. M. A.; Tornos, J. A. Org. Biomol. Chem. 2005, 3, 2741–2749; (i)
Hodgson, D. M.; Hachisu, S.; Andrews, M. D. J. Org. Chem. 2005, 70, 8866–8876;
(j) Scott, M. E.; Lautens, M. Org. Lett. 2005, 7, 3045–3047; (k) Pandey, S. K.;
Orellana, A.; Greene, A. E.; Poisson, J.-F. Org. Lett. 2006, 8, 5665–5668; (l)
Sakaguchi, H.; Tokuyama, H.; Fukuyama, T. Org. Lett. 2007, 9, 1635–1638; (m)
Thuong, M. B. T.; Sottocornola, S.; Prestat, G.; Broggini, G.; Madec, D.; Poli, G.
Synlett 2007, 1521–1524; (n) Chalker, J. M.; Yang, A.; Deng, K.; Cohen, T. Org.
Lett. 2007, 9, 3825–3828; (o) Sakaguchi, H.; Tokuyama, H.; Fukuyama, T. Org.
Lett. 2008, 10, 1711–1714.
see
Scheme 4
(
R
)-2a
Ts
N
(>98% ee
)
(3R, 4R)-4
OTBS
s-BuLi, 14
ClCOOMe
Boc N
Et2O, –78 ˚C
5. (a) Tomooka, K.; Suzuki, M.; Shimada, M.; Yanagitsuru, S.; Uehara, K. Org. Lett.
2006, 8, 963–965; (b) Tomooka, K.; Suzuki, M.; Uehara, K.; Shimada, M.;
6. Tomooka, K.; Komine, N.; Fujiki, D.; Nakai, T.; Yanagitsuru, S. J. Am. Chem. Soc.
2005, 127, 12182–12183.
(3
R
, 4
R
)-8
OTBS
OTBS
MeO2C
Boc N
7. Analytical and semipreparative-scale HPLC were performed with
a chiral
stationary column [CHIRALCEL OD-H (4.6 Â 250 mm or 20 Â 250 mm)], which
was equipped with a UV detector and a CD spectropolarimeter.
8. The half-life of the optical activity of 2a in hexane at 25 °C is 290 h, see Ref.
5b.
+
Boc N
MeO2C
10b
9. Pd(II)-catalyzed Cope rearrangement, see: Overman, L. E.; Jacobsen, E. J. J. Am.
Chem. Soc. 1982, 104, 7225–7231.
(2R
, 3R
, 4
R
)-9b
10. Diastereopurity and enantiopurity were determined by the 1H NMR and HPLC
analyses.
82% (brsm)
9b:10b = 80:20
11. Calculation of TS-1 was performed by PM3 using Spartan.
12. Liotta, R.; Brown, H. C. J. Org. Chem. 1977, 42, 2836–2839.
13. The hydroboration of 4 was found to result in the exclusive formation of 5,
without any detectable formation of the isoprene-moiety-reacted product.
14. We examined a lithiation/deuteration reaction of 1-tosylpyrrolidine as a model
compound, in which only the ortho-deuterated product i was obtained without
(+)-1
any a-nitrogen-deuterated product ii, as shown below.
N
(–)-14
N
1. s-BuLi (5 equiv.),
Et2O-TMEDA
–78 °C
D
D
D
O
Ts
N
S N
Ts N
Scheme 5. Synthesis of (+)-1.
2. D2O
O
i
ii
Acknowledgments
15. Rac-8 was prepared from rac-2a by the above-mentioned method.
16. Yields were determined after methyl esterification (TMSCHN2/MeOH). Regio-
and diastereoselectivities were determined by 1H NMR and HPLC analyses of
the methyl esters.
17. For reviews, see: (a) Hoppe, D.; Hense, T. Angew. Chem., Int. Ed. 1997, 36, 2282–
2316; (b) Beak, P.; Basu, A.; Gallagher, D. J.; Park, Y. S.; Thayumanavan, S. Acc.
Chem. Res. 1996, 29, 552–560; (c) Tomooka, K. J. Synth. Org. Chem. Jpn. 2001, 59,
322–330; (d) Beak, P.; Johnson, T. A.; Kim, D. D.; Lim, S. H. In Topics in
This research was supported in part by a Grant-in-Aid for Scien-
tific Research in Priority Areas (A) ‘Creation of Biologically Func-
tional Molecules’ from the Ministry of Education, Culture, Sports,
Science and Technology, Japan, and The Naito Foundation.
Organometallic Chemistry
Hodgson, D. M., Ed.; Springer, 2003; pp 39–176.
5 (Organolithiums in Enantioselective Synthesis);
Supplementary data
18. (a) Dearden, M. J.; Firkin, C. R.; Hermet, J.-P. R.; O’Brien, P. J. Am.
Chem. Soc. 2002, 124, 11870–11871; (b) Hermet, J.-P. R.; Porter, D. W.;
Dearden, M. J.; Harrison, J. R.; Koplin, T.; O’Brien, P.; Parmene, J.;
Tyurin, V.; Whitwood, A. C.; Gilday, J.; Smith, N. M. Org. Biomol. Chem.
2003, 1, 3977–3988.
Supplementary data associated with this article can be found, in
19. A similar approach for carboxylation at the C2 position in the asymmetric
synthesis of (–)-kainic acid has been reported by Fukuyama and Tokuyama’s
group, see Ref. 4c.
References and notes
1. Murakami, S.; Takemoto, T.; Shimizu, Z. J. Pharm. Soc. Jpn. 1953, 73, 1026–1028.
2. (a) Hashimoto, K.; Shirahama, H. Trends Org. Chem. 1991, 2, 1–32; (b) Cantrell,
B. E.; Zimmerman, D. M.; Monn, J. A.; Kamboj, R. K.; Hoo, K. H.; Tizzano, J. P.;
Pullar, I. A.; Farrell, L. N.; Bleakman, D. J. Med. Chem. 1996, 39, 3617–3624.
3. (a) Coyle, J. T.; Schwarcz, R. Nature 1976, 263, 244–246; (b) MacGeer, E. G.;
Olney, J. W.; MacGeer, P. L. Kainic Acid as a Tool in Neurogiology; Raven: New
York, 1978; (c) Sperk, G. Prog. Neurobiol. 1994, 42, 1–32; (d) Wang, Q.; Yu, S.;
Simonyi, A.; Sun, G. Y.; Sun, A. Y. Mol. Neurobiol. 2005, 31, 3–16.
20.
A
similar reaction using CO2 instead of methylchloroformate gave the
corresponding carboxylic acids with comparable yields and selectivities.
21. Shioiri, T.; Aoyama, T.; Mori, S. Org. Synth. Coll. 1993, Vol. 8, 612–615.
22. (a) Nozaki, H.; Aratani, T.; Toraya, T.; Noyori, R. Tetrahedron 1971, 27, 905–913;
(b) Kerrick, S. T.; Beak, P. J. Am. Chem. Soc. 1991, 113, 9708–9710; (c) Hoppe, D.;
Christoph, G. In The Chemisty of Organolithium Compound; Rappoport, Z., Marek,
I., Eds.; John Wiley & Sons, 2004; pp 1055–1164.