Fluorous Synthesis of Yuehchukene
[6] a) V. Snieckus, Chem. Rev. 1990, 90, 879; b) G. W. Rewcastle,
A. R. Katritzky, Adv. Heterocycl. Chem. 1993, 56, 155.
[7] Most of the typical fluorous tags require methylene spacers
between the perfluoroalkyl chains and the tagging functionali-
ties to reduce the influence of the perfluorated moieties. When
molecules with these tags are exposed to typical lithiation con-
ditions, undesired deprotonation of acidic protons on the
methylene spacers occurs as a problematic side reaction.
.
0.766 mmol) in Et2O (3 mL) was added to MesLi (0.92 mmol) in
Et2O at –78 °C under argon. The mixture was stirred at –40 °C for
3 h. Then 5 (308.5 mg, 2.05 mmol) was added to the mixture, and
the mixture was stirred at room temp. for 18 h. The reaction was
quenched with saturated aqueous NH4Cl solution (2 mL) and the
aqueous layer was extracted with AcOEt (5 mLϫ3). The organic
layer was washed with brine and dried with MgSO4. Concentration
of the organic phase gave the crude product, which was purified by
silica gel column chromatography with n-hexane/AcOEt to afford
1
424.1 mg (67%) of 6 as a solid. H NMR (CDCl3, 400 MHz): δ =
8.21 (s, 1 H), 8.07–8.11 (m, 2 H), 7.73 (d, J = 8.0 Hz, 1 H), 7.55
(t, J = 8.0 Hz, 1 H), 7.46 (d, J = 7.7 Hz, 1 H), 7.31 (dt, J = 1.2,
7.6 Hz, 1 H), 7.23 (t, J = 7.3 Hz, 1 H), 6.80 (s, 1 H), 6.02 (d, J =
5.6 Hz, 1 H), 5.95 (br. s, 1 H), 5.70 (d, 1 H), 2.58 (br. s, 1 H), 2.19
(d, J = 16.7 Hz, 1 H), 1.83 (d, J = 16.7 Hz, 1 H), 1.81 (s, 3 H),
1.06 (s, 3 H), 0.82 (s, 3 H) ppm. 13C NMR (CDCl3, 100 MHz): δ
= 143.8, 142.5, 139.8, 137.3, 136.0, 131.7, 130.1, 129.8, 128.9, 125.5,
125.1, 121.3, 118.1, 114.5, 112.4, 65.6, 45.7, 33.8, 26.2, 26.0, 23.3
[8] 3-(Perfluorooctyl)benzenesulfonyl chloride: S. Cerezo, J. Cor-
tes, D. Galvan, E. Lago, C. Marchi, E. Molins, M. Moreno-
Manas, R. Pleixats, J. Torrejon, A. Vallribera, Eur. J. Org.
Chem. 2001, 329.
[9] a) Y.-C. Kong, K.-F. Cheng, R. C. Cambie, P. G. Waterman, J.
Chem. Soc. Chem. Commun. 1985, 47; b) T. W. T. Leung, G.
Cheng, C. H. Chui, S. K. W. Ho, F. Y. Lau, J. K. J. Tjong,
T. C. C. Poon, J. C. O. Tang, W. C. P. Tse, K. F. Cheng, Y. C.
Kong, Chemotherapy 2000, 46, 62.
ppm. IR (neat): ν = 2962, 1374, 1198 cm–1. EIMS: m/z (%) = 825
˜
(10) [M+] 144 (100). HRMS calcd. for C32H24F17NO3S: 825.1205;
found 825.1518.
Supporting Information (see also the footnote on the first page of
this article): Experimental procedures and spectroscopic data.
[10] a) D. L. Comins, D. H. LaMunyon, Tetrahedron Lett. 1988, 29,
773; b) Y. Kondo, M. Asai, T. Miura, M. Uchiyama, T. Sakam-
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[11] Other metallic bases were also tested, but MesLi in diethyl
ether was proved to be the best reagent for our purpose; see
Supporting Information for details.
Acknowledgments
This work was partly supported by the Ministry of Education, Sci-
ence, Sports and Culture, Japan by a Grant-in Aid for Scientific
Research (no. 19390002, no. 19790003) and a grant from the Sumi-
tomo Foundation and the Yamada Science Foundation.
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Received: June 7, 2007
Published Online: August 10, 2007
Eur. J. Org. Chem. 2007, 4635–4637
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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