Communications
639 cmꢀ1; elemental analysis calcd (%) for C21H37F3IO11.5S (689.50): C
36.58, H 5.41; found: C 36.29, H 5.14.
bridge CB21EZ, UK; fax: (+ 44)1223-336-033; or deposit@
ccdc.cam.ac.uk).
8: Potassium trans-1-decenyl trifluoroborate (9.9 mg, 0.04 mmol)
was added at room temperature under nitrogen to a solution of 4a
(39 mg, 0.059 mmol) in H2O (2.5 mL), and the mixture was stirred for
3 h. The mixture was extracted with CH2Cl2 four times. The combined
organic phases were filtrated and evaporated under an aspirator
vacuum to give an oil, which was washed several times with hexane
and then with hexane/diethyl ether by decantation at 08C to give a
1:1.3 mixture of trans-1-decenyl(phenyl)(trifluoromethanesulfonato)-
l3-iodane and [18]crown-6 (30.6 mg, 0.036 mmol, 90%) as a white
powder. Recrystallization from dichloromethane/ethyl acetate/
hexane at ꢀ308C gave 8 as colorless needles: m.p. 71.5–728C;
1H NMR (400 MHz, CDCl3): d = 7.95 (d, J = 8.2 Hz, 4H), 7.70 (t,
J = 7.3 Hz, 2H), 7.54 (dd, J = 8.2, 7.3 Hz, 4H), 6.85–6.72 (m, 4H), 3.69
(s, 24H), 2.34 (q, J = 7.3 Hz, 4H), 1.44 (quint, J = 7.3 Hz, 4H), 1.32–
1.19 (m, 20H) 0.88 ppm (t, J = 6.8 Hz, 6H); IR (nujol): n˜ = 3042, 1563,
1265, 1223, 1152, 1101, 1031, 956, 838, 754, 638 cmꢀ1; elemental
analysis calcd (%) for C46H72F6I2O12S2 (1249.03): C 44.23, H 5.81;
found: C 44.55, H 5.93.
[10] a) N. W. Alcock, Adv. Inorg. Chem. Radiochem. 1972, 15, 1; b) J.
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[11] M. Ochiai, T. Suefuji, K. Miyamoto, N. Tada, S. Goto, M. Shiro,
S. Sakamoto, K. Yamaguchi, J. Am. Chem. Soc. 2003, 125, 769.
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W. Chen, M. Kida, Tetrahedron Lett. 1997, 38, 6709.
[13] a) M. Ochiai, K. Miyamoto, T. Suefuji, S. Sakamoto, K.
Yamaguchi, M. Shiro, Angew. Chem. 2003, 115, 2241; Angew.
Chem. Int. Ed. 2003, 42, 2191; b) M. Ochiai, K. Miyamoto, T.
Suefuji, M. Shiro, S. Sakamoto, K. Yamaguchi, Tetrahedron 2003,
59, 10153.
[14] R. M. Moriarty, J. S. Khosrowshahi, O. Prakash, Tetrahedron
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[15] a) SHELXS86: G. M. Sheldrick in Crystallographic Computing 3
(Eds.: G. M. Sheldrick, C. Kruger, R. Goddard), Oxford
University Press, Oxford, 1985, p. 175; b) DIRDIF99: P. T.
Beurskens, G. Admiraal, G. Beurskens, W. P. Bosman, R.
de Gelder, R. Israel, J. M. M. Smits, The DIRDIF-99 program
system, Technical Report of the Crystallography Laboratory,
University of Nijmegen, The Netherlands, 1999.
Received: July 21, 2004
Keywords: crown compounds · hypervalent compounds ·
.
iodine · Koser reagent · oxidation
[1] a) G. F. Koser, Aldrichimica Acta 2001, 34, 89; b) R. M. Mor-
iarty, R. K. Vaid, G. F. Koser, Synlett 1990, 365; c) V. V.
Zhdankin, P. J. Stang, Chem. Rev. 2002, 102, 2523; d) A.
Varvoglis, The Organic Chemistry of Polycoordinated Iodine,
VCH, New York, 1992; e) For hypervalent iodine chemistry, see:
T. Wirth, Top. Curr. Chem. 2003, 224.
[2] H. W. Richter, B. R. Cherry, T. D. Zook, G. F. Koser, J. Am.
Chem. Soc. 1997, 119, 9614.
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Martin, M. P. Muldowney, N. C. Norman, A. G. Orpen, J. Chem.
Soc. Chem. Commun. 1994, 2367.
[4] We measured the solubility of iodosylbenzene (2.3 10ꢀ3 m) in
1
water at 258C by H NMR spectroscopy. The ylide-type struc-
ture PhI+(OH2)Oꢀ was proposed for monomeric iodosylbenzene
dissolved in water at near pH 7.[2]
[5] a) T. Wirth, U. H. Hirt, Tetrahedron: Asymmetry 1997, 8, 23;
b) U. H. Hirt, M. F. H. Schuster, A. N. French, O. G. Wiest, T.
Wirth, Eur. J. Org. Chem. 2001, 1569.
[6] M. Ochiai, K. Miyamoto, M. Shiro, T. Ozawa, K. Yamaguchi, J.
Am. Chem. Soc. 2003, 125, 13006.
[7] K. S. Daub, B. Habermann, T. Hahn, L. Teich, K. Eger, Eur. J.
Org. Chem. 2004, 894.
[8] T. Kitamura, R. Furuki, H. Taniguchi, P. J. Stang, Tetrahedron
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[9] Crystal data for 4a: C19H32F3IO11S, colorless block of dimensions
3
¯
0.20 0.15 0.07 mm , triclinic, P1 (No. 2), a = 9.058(5), b =
10.820(7), c = 13.99(1) , b = 93.95(2)8, V= 1307(1) 3, Z = 2,
1calcd = 1.657 gcmꢀ3. Data collected on a Rigaku RAXIS-RAPID
imaging plate diffractometer with MoKa radiation (l =
0.71075 ) at T= 93 K, 2qmax = 59.88, 14070 reflections mea-
sured, of which 7318 unique (Rint = 0.023), m = 13.80 cmꢀ1. The
structure was solved by direct methods[15a] and expanded by
using Fourier techniques,[15b] R = 0.042, Rw = 0.090. Some hydro-
gen atoms were refined isotropically, some were refined by using
the riding model, and the rest were included in fixed positions.
CCDC-242208 contains the supplementary crystallographic data
for this paper. These data can be obtained free of charge via
bridge Crystallographic Data Centre, 12, Union Road, Cam-
78
ꢀ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2005, 44, 75 –78