L.-L. Shen, H.-S. Mun, J.-H. Jeong
SHORT COMMUNICATION
added to a solution of 10-hydroxyundecanoic acid (188.2 mg,
Acknowledgments
1.0 mmol) in toluene, and the solution was heated at reflux for 28 h.
After cooling the mixture to room temperature, the solvent was
removed by evaporation, and the residue was separated on a flash
chromatography column (eluent = 20:1 n-hexane:ethyl acetate) to
yield 116 mg of 7 (68%) and 42 mg of 5 (25%).
This work was supported by a Korea Research Foundation grant
funded by the Korean government (MOEHRD; KRF-2005-041-
E00499) and the Seoul R&BD Programme (10524). We thank Prof.
Park Hyun-ju (College of Pharmacy, Sungkyunkwan University)
for calculating the molecular energies of compounds 13 and 14.
The Current Method: Trimethylaluminium (5 mL of a 2 m solution,
1
0 mmol) in toluene was added to a 50-mL side-arm flask contain-
[
1] L. I. Zakharkin, V. V. Gavrilenko, Russ. Chem. Bull. 1960, 9,
ing selenium powder (820.0 mg, 10.4 mmol). When the selenium
powder had reacted completely, the resulting mixture was cooled
1294–1300.
[
[
[
2] A. P. Kozikowski, A. Ames, Tetrahedron 1985, 41, 4821–4834.
3] A. P. Kozikowski, A. Ames, J. Org. Chem. 1978, 43, 2735–2737.
4] H. Zhu, J. Chai, H. W. Roesky, M. Noltemeyer, H.-G. Schmidt,
J. M. Denis Vidovic, Eur. J. Inorg. Chem. 2003, 3113–3119.
5] W. Zheng, N. C. Mösch-Zanetti, H. W. Roesky, M. Noltemeyer,
M. Hewitt, H.-G. Schmidt, T. R. Schneider, Angew. Chem. Int.
Ed. 2000, 39, 4276–4279.
to room temperature. An aliquot of Me
.0 mmol) was transferred by syringe to a solution containing
methyl 10-hydroxyundecanoate (188.2 mg, 1.0 mmol) in toluene
10 mL) at 0 °C. After 28 h of heating at reflux, the yellow solution
2
SeAlMe (0.05 mL,
1
(
[
was warmed to room temperature over a period of 30 min and
treated with sodium sulfate. The solution was then diluted with
dichloromethane, washed with water six times and treated with so-
dium hydrogen carbonate. The solution was then dried with brine
and anhydrous magnesium sulfate. The solvent was removed under
vacuum from the yellow solution, and the residue was separated by
using a flash chromatography column with the same eluent as
[6] H. Yamamoto, K. Oshima in Main Group Metals in Organic
Synthesis, Chapter 6. Aluminum in Organic Synthesis, Wiley-
VCH, Weinheim 2005, p. 189–207.
[
7] a) E. J. Corey, D. J. Beames, J. Am. Chem. Soc. 1973, 95, 5829–
5
831; b) E. J. Corey, A. P. Kozikowski, Tetrahedron Lett. 1975,
16, 925–928.
–
1
above to yield 124 mg of 5 (71%). FTIR (KBr): ν˜ = 1728.87 cm .
[
[
8] C. Elschenbroich, A. Salzer in Organometallics: A Concise In-
troduction, Wiley-VCH, Weinheim, 1992.
1
H NMR (CDCl
m, 4 H, 2CH ), 2.32 (t, J = 6.8 Hz, 2 H, CH
) ppm. 13C NMR (CDCl
, 100 MHz): δ = 25.52 (CH
6.18 (CH ), 28.76 (CH ), 29.08 (CH ), 29.23 (CH ), 29.55 (CH
9.82 (CH ), 34.99 (CH ), 64.14 (CH ), 174.05 (CH
3
, 400 MHz): δ = 1.30 (br. m, 12 H, 6CH
2
), 1.61
(
2
2
), 4.11 (t, J = 5.6 Hz,
9] C. Paulmier in Selenium Reagents and Intermediates in Organic
Synthesis, Pergamon Press, Oxford, 1986, p. 65–67.
2
2
2
H, CH
2
3
2
),
), [10] For recent review on selenol esters: a) A. Ogawa, N. Sonoda,
2
2
2
2
2
“Selenoesters of all oxidation states”, in Comprehensive organic
2
2
2
2
) ppm. ESI-
synthesis (Ed.: B. M. Trost), Elsevier, Amsterdam, 1992, vol. 7,
chapter 2.6, p. 461–472; b) A. Ogawa, N. Sonoda, “Acylsulfur, -
selenium, or -tellurium functions”, in Comprehensive Organic
Functional Group Transformations II (Eds.: A. R. Katritzky,
R. J. K. Taylor), Elsevier, Amsterdam, 1995, chapter 5.05, p.
MS: calcd. 340.26; found 340.91.
Norpyrenophorin (4): An aliquot of Me
.0 mmol) was transferred by syringe to a solution containing 12
436.5 mg, 2.0 mmol) in toluene (10 mL) at 0 °C. After heating at
2
SeAlMe (0.1 mL,
2
(
233–241.
reflux for 28 h, the yellow solution was warmed to room tempera-
ture over a period of 30 min and treated with moist sodium sulfate.
The solution was then diluted with dichloromethane, washed six
times with water and treated with sodium hydrogen carbonate. The
solution was then dried with brine and anhydrous magnesium sul-
fate. The solvent was removed from the yellow solution by vacuum
evaporation, and the residue was separated by using a flash
[
11] For recent review on macrolactonisation: a) B. M. Trost, Chem.
Nat. Compd. 1978, 14, 787; b) R. Ballini, M. Petrini, ARKI-
VOC 2009, 9, 195–223; c) P. G. Baraldi, A. Barco, S. Benetti,
F. Moroder, G. P. Pollini, D. Simoni, J. Org. Chem. 1983, 48,
1297–1302; d) A. Furstner, O. R. Thiel, L. Ackermann, Org.
Lett. 2001, 3, 449–451; e) R. V. Hoffman, T. Patonay, N. K.
Nayyar, J. Tao, Tetrahedron Lett. 1996, 37, 2381–2384; f) Y.
Kobayashi, M. Nakano, G. B. Kumar, K. Kishihara, J. Org.
Chem. 1998, 63, 7505–7515; g) J. W. Labadie, J. K. Stille, Tetra-
hedron Lett. 1983, 24, 4283–4286; h) L. Maciejewski, M. Mar-
tin, G. Ricart, J. Brocard, Synth. Commun. 1988, 18, 1757–
1762; i) Y. Matsushita, H. Furusawa, T. Matsui, M. Nakayama,
Chem. Lett. 1994, 23, 1083–1084; j) M. Petrini, R. Ballini, G.
Rosini, E. Marotta, Tetrahedron 1986, 42, 151–154; k) K. S.
Rao, D. S. Reddy, K. Mukkanti, M. Pal, J. Iqbal, Tetrahedron
Lett. 2006, 47, 6623–6626; l) T. Sugai, O. Katoh, H. Ohta, Tet-
rahedron 1995, 51, 11987–11998; m) J. S. Yadav, U. V.
Subba Reddy, B. V. Subba Reddy, Tetrahedron Lett. 2009, 50,
chromatography column (eluent = 5:1 n-hexane/ethyl acetate) to
1
yield 13 as a colourless liquid. H NMR (CDCl
3
, 400 MHz): δ =
), 4.16 (t, J =
), 6.12 (d, J = 16.0 Hz, 1 H, CH), 6.57 (d, J =
6.0 Hz, 1 H, CH) ppm.
1
5
1
.57 (m, J = 5.0 Hz, 4 H, 2CH
2 3
), 3.18 (s, 3 H, CH
.0 Hz, 2 H, CH
2
The colourless liquid was dissolved in a 3:1:1 solution of AcOH/
O/THF, heated at reflux for 1 h, quenched with sodium hydro-
gen carbonate and diluted with dichloromethane. The solution was
washed three times and treated with brine, dried with MgSO , fil-
H
2
4
5
984–5986; n) R. Ballini, L. Barboni, D. Fiorini, A. Palmieri,
tered and concentrated to obtain a colourless liquid. After purifica-
tion by silica gel chromatography (eluent = 1:1 n-haxane:ethyl acet-
ate), 151 mg of white powder was obtained with 54% yield over two
M. Petrini, ARKIVOC 2006, 6, 127–152; o) A. Barco, S. Be-
netti, C. De Risi, P. Marchetti, G. P. Pollini, V. Zanirato, Tetra-
hedron Lett. 1998, 39, 1973–1976; p) K. J. Davis, U. T.
Bhalerao, B. V. Rao, Indian J. Chem. Sect. B 2001, 40, 656–
661; q) C. W. Lee, R. H. Grubbs, J. Org. Chem. 2001, 66, 7155–
–1 1
3
steps. FTIR (KBr): ν˜ = 1731.76, 1645.95 cm . H NMR (CDCl ,
4
6
1
00 MHz): δ = 1.37 (m, J = 7.16 Hz, 2 H, CH
.96 Hz, 2 H, CH ), 4.30 (t, J = 7.12 Hz, 2 H, CH
6.2 Hz, 1 H, CH), 7.02 (d, J = 16.2 Hz, 1 H, CH) ppm. C NMR
, 100 MHz): δ = 29.70 (CH ), 36.89 (CH ), 53.42 (CH ),
28.86 (CH), 139.89 (CH) ppm. EI-MS: calcd. for [M + H] 281.09;
2
), 2.84 (t, J =
7
158; r) M. D. Ronsheim, C. K. Zercher, J. Org. Chem. 2003,
2
2
), 6.67 (d, J =
13
68, 4535–4538; s) M. Vrettou, A. A. Gray, A. R. E. Brewer,
A. G. M. Barrett, Tetrahedron 2007, 63, 1487–1536; t) J. E. Bal-
dwin, R. M. Adlington, S. H. Ramcharitar, Synlett 1992, 875–
(CDCl
3
2
2
2
+
1
8
77; u) A. Barco, S. Benetti, C. D. Risi, G. P. Pollini, V. Zanir-
found 281.12.
ato, Tetrahedron 1995, 51, 7721–7726; v) S. Hatakeyama, K.
Satoh, K. Sakurai, S. Takano, Tetrahedron Lett. 1987, 28,
Supporting Information (see footnote on the first page of this arti-
2717–2720; w) N. Machinaga, C. Kibayashi, Tetrahedron Lett.
1
13
cle): H NMR, C NMR, IR and mass spectra of the solid-phase
reaction and the synthesis of norpyrenophorin are presented.
1993, 34, 841–844; x) R. S. Mali, M. Pohmakotr, B. Weidmann,
D. Seebach, Liebigs Ann. Chem. 1981, 12, 2272–2284; y) J. No-
6898
www.eurjoc.org
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2010, 6895–6899