Mi Young Yoon et al.
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[6] However, it has recentlybeen suggested byTunge et al.
that the Fujiwara hydroarylation occurs rather via typi-
cal Friedel–Crafts alkenylation pathway; see: J. A.
Tunge, L. N. Foresee, Organometallics 2005, 24, 6440.
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H2O (9 mL, 0.5 mmol) and 5a (0.5 mL). The mixture was
stirred at 858C for 4 h. Standard work-up gave 6-d5–6 as a
colorless solid; yield: 79 mg (79%) of The H NMR spec-
trum of 6-d5–6 showed that the intensities of the vinyl proton
(at 6.17 ppm as a quartet) and methyl protons (doublet at
1.76 ppm for 6-d5 and singlet at 1.75 ppm for 6-d6) were in a
ratio of 1.00 : 3.99. The GC/MS confirmed the formation of
five-deuterium-incorporated adduct 6-d5 (m/z [M+]=199.1,
200.1). These results revealed that 75% of the H from H2O
and 25% of D from the aromatic substrate were incorporat-
ed into vinyl part of product 6-d5–6
Reaction of benzene with 1-phenyl-1-propyne in the pres-
ence of D2O and 5a: Under an argon atmosphere, 1-phenyl-
1-propyne (58.0 mg, 0.5 mmol) was added to a mixture of
[9] T. Tsuchimoto, T. Maeda, E. Shirakawa, Y. Kawakami,
Chem. Commun. 2000, 1573.
[10] For reviews of Friedel–Crafts alkylation reactions, see:
a) Friedel–Crafts and Related Reactions, Vol. II, Part 1,
(Ed.: G. A. Olah), Wiley-Interscience, New York, 1964;
b) Friedel–Crafts Alkylation Chemistry. A Century of
Discovery, (Eds.: R. M. Roberts, A. A. Khalaf),
Dekker, New York, 1984; c) G. A. Olah, R. Krishna-
murit, G. K. S. Prakash, in: Friedel–Crafts Alkylations
in Comprehensive Organic Synthesis, (Eds.: B. M. Trost,
I. Fleming), Pergamon Press, Oxford, 1991.
[11] For recent reviews on ionic liquids, see: a) C. E. Song,
Ann, Rep. Prog. Chem. Sect. C. 2005, 101, 143; b) C. E.
Song, M. Y. Yoon, D. S. Choi, Bull. Korean Chem. Soc.,
2005, 26, 1321; c) C. E. Song, in: Methodologies in
Asymmetric Catalysis, (Ed.: S. V. Malhotra), ACS Sym-
posium Series 880, 2004, 145; d) C. E. Song, Chem.
Commun. 2004, 1033; e) J. Dupont, R. F. de Souza,
P. A. Z. Suarez, Chem. Rev. 2002, 102, 3667; f) C.
Gordon, Appl. Catal. A.: General 2001, 222, 101; g) R.
Sheldon, Chem. Commun. 2001, 2399; h) P. Wassersc-
heid, W. Keim, Angew. Chem. Int. Ed. 2000, 39, 3772;
i) T. Welton, Chem. Rev. 1999, 99, 2071.
[12] Our recent examples: a) C. E. Song, W. H. Shim, E. J.
Roh, J. H. Choi, Chem. Commun. 2000, 1695; b) C. E.
Song, E. J. Roh, Chem. Commun. 2000, 837; c) C. E.
Song, W. H. Shim, E. J. Roh, S.-g. Lee, J. H. Choi,
Chem. Commun. 2001, 1122; d) D. W. Kim, C. E. Song,
D. Y. Chi, J. Am. Chem. Soc. 2002, 124, 10278; e) D. W.
Kim, C. E. Song, D. Y. Chi, J. Org. Chem. 2003, 68,
4281; f) E. J. Kim, S. Y. Ko, C. E. Song, Helv. Chim.
Acta 2003, 86, 894; g) S.-g. Lee, Y. J. Zhang, P. Z. Yu,
H. Yoon, C. E. Song, J. H. Choi, J. Hong, Chem.
Commun. 2003, 2624; h) C. E. Song, D. Jung, S. Y.
Chung, E. J. Roh, S.-g. Lee, Angew. Chem. Int. Ed.
2004, 43, 6183.
Sc(OTf)3 (24.6 mg, 0.05 mmol), benzene (2 mL), D2O (9 mL,
R
0.5 mmol) and 5a (0.5 mL). The mixture was stirred at 858C
for 4 h. Standard work-up gave 6-d0~1 as a colorless solid;
yield: 68 mg (70%). The 1H NMR spectrum of 6-d0–1
showed that the intensities of the vinyl proton (at 6.17 ppm
as a quartet) and methyl protons (doublet at 1.76 ppm for 6-
d0 and singlet at 1.75 ppm for 6-d1) were in a ratio of
1.00:6.17. The GC/MS confirmed the formation of five-deu-
terium-incorporated adduct 6-d1 (m/z [M+]=195.1, 196.1).
These results revealed that 52% of the D from D2O and
48% of H from the aromatic substrate were incorporated
into vinyl part of product 6-d0–1
Acknowledgements
This work was supported by a Korea Research Foundation
Grant (KRF-2005-005-J11901) funded by MOEHRD, and by
grants R01-2006-000-10426-0 (KOSEF) and R11-2005-008-
00000-0 (SRC program of MOST/KOSEF).
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[13] Ionic liquids 5a–e were purchased from C-Tri Co., Ltd.,
callypure, nearlychloride-free ( <10 ppm) and their
water content was <200 ppm (determined byKarl-
Fisher titration).
[14] Recently, Rogers and co-workers reporÀted the instabili-
tyof the ionic liquids counterion PF
towards mois-
6
ture, which resulted in hydrolysis and the formation of
HF, see: R. P. Swatloski, J. D. Holbrey, R. D. Rogers,
Green Chem. 2003, 5, 361. Therefore, to examine the
possible catalytic effect of HF on this reaction, we also
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carried out the reaction onlyin [bmim]
A
mixture of [bmim][SbF6]and water (1:1, v/v), without
AHCTREUNG
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Adv. Synth. Catal. 2007, 349, 1725 – 1737