2060
C. Tanyeli, E. Turkut / Tetrahedron: Asymmetry 15 (2004) 2057–2060
4
6
.5. Synthesis of (ꢁS,5S±)()±)7)oꢀaꢂicyclo[-.2.ꢁ]oct)2)en)
)one (ꢁS,5S±)()±)4
References and notes
1
2
. Trost, B. M. Science ꢁ985, 227, 908.
. (a) Ladner, W. E.; Whitesides, G. M. J. Am. Chem. Soc.
To
a solution of (1S,2S,5S)-())-2-iodo-7-oꢁabicy-
ꢁ
ꢁ
984, 106, 7250; (b) Zaks, A.; Klibanov, A. M. Science
984, 224, 1249; (c) Zaks, A.; Klibanov, A. M. Proc. Natl.
Acad. Sci. U.S.A. ꢁ985, 82, ꢀ192; (d) Sweers, H. M.;
Wong, C.-H. J. Am. Chem. Soc. ꢁ986, 108, 6421; (e)
Wang, Y.-F.; Wong, C.-H. J. Org. Chem. ꢁ988, 53, ꢀ127;
clo[ꢀ.2.1]octan-6-one - (1.01 g, 4.01 mmol) in 28 mL
THF, DBU (0.90 mL, 6.0 mmol) was added and the
miꢁture stirred at refluꢁ for 8 h. Upon being cooled to
room temperature, the miꢁture was poured into 0.5 M
HCl and eꢁtracted with ether (ꢀ · 50 mL). The organic
phase was washed with brine (50 mL), dried over anhy-
(f) Faber, K. Biotransformations in Organic Chemistry, ꢀrd
ed.; Springer: Heidelberg, 1997.
drous MgSO
4
, concentrated in vacuo. The crude product
was purified by flash column chromatography to afford
ꢀ. Nair, V.; Buenger, G. S. J. Org. Chem. ꢁ990, 55, ꢀ695–
ꢀ697.
4. Herdewijn, P.; De Clercq, E. Bioorg. Med. Chem. Lett.
product ())-4. (0.45 g, 91%) as a colorless oil; R (EtOAc/
f
20
2
00ꢁ, 11, 1591–1597.
heꢁane 1:ꢀ) 0.26; >99% ee ½a ¼ )201.2 (c 4.0 in CHCl
ꢀ
),
D
10b
20
5. Barral, K.; Halfon, P.; Pepe, G.; Camplo, M. Tetrahedron
Lett. 2002, 43, 81–84.
lit. ½a ¼ )182.1 (c 4.8 in CHCl
ꢀ
). All spectroscopic
D
data are in accordance with the literature values.
9c
6
. (a) Starzl, T. E.; Fung, J.; Venkataramman, R.; Todo, S.;
Demetris, A. J.; Jain, A. Lancet ꢁ989, 1000–1004; (b)
Siekierka, J. J.; Hung, S. H. Y.; Poe, M.; Lin, C. S.; Sigal,
N. H. Nature ꢁ989, 341, 755–757; (c) Harding, M. W.;
Galat, A.; Uehling, D. E.; Schreiber, S. L. Nature ꢁ989,
4
.6. Synthesis of (ꢁS,5S±)()±)5)(hydroꢀymethyl±)2)
cycloheꢀen)ꢁ)ol (ꢁS,5S±)()±)5
3
692.
41, 758–760; (d) Freedman, R. B. Nature ꢁ989, 341,
(
ꢀ
1S,5S)-())-7-Oꢁabicyclo[ꢀ.2.1]oct-2-en-6-one 4 (0.40 g,
.1ꢀ mmol) was dissolved in THF (10 mL) and added
dropwise to LiAlH (0.16 g, ꢀ.1ꢀ mmol) dissolved in
O (0.1 mL),
7. (a) Kino, T.; Hatanaka, H.; Hashimoto, M.; Nishiyama,
M.; Goto, T.; Okuhara, M.; Kohsaka, M.; Aoki, H.;
Imanaka, H. J. Antibiot. ꢁ987, 40, 1249–1255; (b) Tanaka,
H.; Kuroda, A.; Marusawa, H.; Hatanaka, H.; Kino, T.;
Goto, T.; Hashimoto, M. J. Am. Chem. Soc. ꢁ987, 109,
4
THF (ꢀ0 mL) at 0 ꢁC and stirred for 1 h. H
aq NaOH (0.1ꢀ mL) (15%, w/w), and H O (0.1 mL) were
2
2
added sequentially, and the miꢁture was allowed to
reach room temperature with stirring for 1 h. The salts
were removed by filtration, and the solution was dried
over MgSO
5
5
0ꢀ1–50ꢀꢀ.
8
. (a) Jones, T. K.; Mills, S. G.; Reamer, R. A.; Askin, D.;
Desmond, R.; Volante, R. P.; Shinkai, I. J. Am. Chem.
Soc. ꢁ989, 111, 1157–1159; (b) Nakatsuka, M.; Ragan, J.
A.; Sammakia, T.; Smith, D. B.; Uehling, D. E.; Schreiber,
S. L. J. Am. Chem. Soc. ꢁ990, 112, 558ꢀ–5601; For a
recent listing of synthetic approaches to fragments of FK-
4
and concentrated in vacuo to give product
. (0.40 g, quantitative chemical yield) as a colorless
9b
20
semi-solid; ½a ¼ )20.4 (c 1.5 in MeOH), lit. for
D
20
(
ꢀ
(
1R,5R)-(+)-5 ½a ¼ )20.ꢀ (c 1.46 in MeOH); mmaꢁ (neat)
D
5
06, see: (c) Villlobos, A.; Danishefsky, S. J. J. Org. Chem.
990, 55, 2776–2786; (d) Chini, M.; Crotti, P.; Macchia,
F.; Pineschi, M. Tetrahedron ꢁ992, 48, 5ꢀ9–544.
H ꢀ
590, ꢀ040, 1ꢀ90, 1090; d (400 MHz, CDCl ): 5.64–5.7ꢀ
ꢁ
1H, m, CHOHCH@CH), 5.58–5.6ꢀ (1H, m,
CH@CHCH ), 4.29–4.ꢀ9 (1H, m, CHOH), ꢀ.40–ꢀ.5ꢀ
2
9
. (a) Smith, A. B., III; Hale, K. J.; Laakso, L. M.; Chen, K.;
Riera, A. Tetrahedron Lett. ꢁ989, 30, 696ꢀ–6966; (b)
Linde, R. G., II; Egbertson, M.; Coleman, R. S.; Jones, A.
B.; Danishefsky, S. J. J. Org. Chem. ꢁ990, 55, 2771–2776;
(
2H, m, CH
CH OH), 1.96–2.11 (2H, m, CHOHCH
1H, m, @CHCH H ), 1.65–1.77 (1H, m, @CHCH H ),
2
OH), 2.65–ꢀ.05 (2H, br s, CHOH and
2
2
), 1.77–1.88
(
1
1
a
b
a
b
.15–1.27 (1H, m, CHCH
2
C ꢀ
OH); d (100.6 MHz, CDCl ):
(
c) Marshall, J. A.; Shiping, X. J. Org. Chem. ꢁ995, 60,
72ꢀ0–72ꢀ7.
0. (a) Ceder, O.; Hansson, B. Acta Chem. Scand. ꢁ970, 24,
69ꢀ; (b) Martin, S. F.; Dappen, M. S.; Dupre, B.;
Murphy, C. J.; Colapnet, J. A. J. Org. Chem. ꢁ989, 54,
ꢀ1.4, 128.5, 67.4, 67.5, ꢀ5.56, ꢀ5.5ꢀ, 28.4.
1
2
2
ꢁ
209–2216; (c) Trost, B. M.; Kondo, Y. Tetrahedron Lett.
99ꢁ, 32, 161ꢀ–1616.
Acknowledgements
1
1
1. Poll, T.; Sobczak, A.; Hartmann, H.; Helmchen, G.
Tetrahedron Lett. ꢁ985, 26, ꢀ095–ꢀ098.
2. Karig, G.; Fuchs, A.; B u€ sing, A.; Brandstetter, T.;
Scherer, S.; Bats, J. W.; Eschenmoser, A.; Quinkert, G.
Helv. Chim. Acta 2000, 83, 1049.
We thank the Turkish Scientific and Technical Research
Council for a grant [no. TBAG-2244(102T169)] and
Turkish State Planning Organization for a grant (no.
BAP-07-02-DPT-2002 K120540-04).