2852
S. Y. Park et al. / Tetrahedron Letters 46 (2005) 2849–2852
electron withdrawing groups (F, NO , CN) induce mix-
2
ture of homo- and cross-coupling products.
11. Lipshutz, B. H.; Tomioka, T.; Sato, K. Synlett, 2001,
Special issue, 970.
1
1
2. Lipshutz, B. H. Adv. Synth. Catal. 2001, 343, 313.
3. Lipshutz, B. H.; Tasler, S.; Chrisman, W.; Spliethoff, B.;
Tesche, B. J. Org. Chem. 2002, 67, 1177.
No positional effect of the substituents on the reaction
rate was observed (runs 2, 3, 4 and 5, 6, 7). This repre-
sents that no size discrimination can be done by this sys-
tem and this may be due to solution-based catalysis of
this system.
1
4. Jun, S.; Joo, S. H.; Ryoo, R.; Kruk, M.; Jaroniec, M.; Liu,
Z.; Ohsuna, T.; Terasaki, O. J. Am. Chem. Soc. 2000, 122,
1
0712.
1
5. Procedure for preparing Ni/nano C: The synthesis of
mesoporous silica template, SBA-15, was performed
1
4
Further study is on progress to understand the unusual
nature of this catalytic system.
following the procedures described elsewhere. In case
of CMK-3, the calcined SBA-15and sucrose were used as
the template and the carbon source, respectively. The
mesopores of the SBA-15(10 g) were filled with the
mixture of the sucrose (12.5g), sulfuric acid (1.4 g) and
water (50 g) by impregnation method. The mixtures were
dried at 373 K and subsequently at 433 K, and then
impregnation/drying step was repeated once more. The
carbonization was carried out with heating to 1173 K
under nitrogen flow, and finally, the silica templates were
dissolved at room temperature in water/ethanol solution
of NaOH.
Acknowledgements
Authors are grateful for the financial support from Inha
University (2004) and I.-M.L. appreciates the invita-
tional fellowship supported by Korea Science and Engi-
neering Foundation (KOSEF) and Japan Society for the
Promotion of Science (JSPS) (2004).
Ni/nano C was prepared by wetness impregnation of
Ni(NO ) into the CMK-3. Typically, 5g of the CMK-3
Supplementary data
3
2
was slurried in the aqueous solution containing 2.49 g of
Ni(NO Æ6H O for about 30 min at room temperature.
Subsequently, the water was completely evaporated at
33 K by using a rotary evaporator and dried in an oven
3
)
2
2
3
for 24 h at 373 K.
1
6. General procedures for coupling of aryl chlorides with
RMgX: To a flame-dried 100 ml of round bottomed flask
under nitrogen at room temperature were added Ni(II)/
nano C (5mg). Dry THF (20 ml) was added via syringe and
the slurry was stirred for 20 min. An aryl chloride
(1.0 mmol) was added dropwise with stirring and then,
excess Grignard reagent (1.1 mmol) in 20 ml of THF was
slowly added at room temperature. The mixture was heated
to reflux for the appropriate time. The reaction was
References and notes
. (a) Negishi, E. I.; Liu, F. In Metal-Catalyzed Cross-
1
Coupling Reactions; Diedrich, F., Stang, P. J., Eds.;
Wiley–VCH: Weinheim, 1998; pp 1–48; (b) Herrmann,
W. A. In Applied Homogeneous Catalysis with Organome-
tallic Compounds; Cornils, B., Herrmann, W. A., Eds.;
Wiley–VCH: Weinheim, 1996; pp 764–765; (c) Kumada,
M. Pure Appl. Chem. 1980, 52, 669–679; (d) Yamamura,
M.; Moritani, I.; Murahashi, S. J. Organomet. Chem.
1
monitored by H NMR after sampling 1 ml of solution
every 5min. After completion of reaction, methanol (5ml)
was then added and the slurry was stirred so as to quench
excess Grignard reagent. The crude mixture was filtered
through a short silica column (1 cm) on the glass frit and the
filter cake further washed with methanol and THF. Solvents
were then removed under reduced pressure and column
chromatography on silica gel gave the purified product.
1975, 91, C39–C42.
2
. (a) Tamao, K.; Sumitani, K.; Kumada, M. J. Am. Chem.
Soc. 1972, 94, 4374; (b) Kumada, M.; Tamao, K.;
Sumitani, K. Org. Synth. 1978, 58, 127.
. Corriu, R. J. P.; Masse, J. P. J. Chem. Soc., Chem.
Commun. 1972, 144.
. Tsuji, J. Palladium Reagents and Catalysis; Wiley: Chich-
ester, 1995.
. (a) Dai, C.; Fu, G. C. J. Am. Chem. Soc. 2001, 123, 2719;
3
4
5
0
1
2,3,4,5,6-Pentafluoro-4 -methoxydiphenylmethane:
NMR (199.976 MHz, CDCl ) d 7.32 (d, 2H), 6.85(d, 2H),
3.81 (s, 2H), 3.79 (s, 3H); C NMR (50.289 MHz, CDCl ) d
163.2, 142.3, 137.5, 132.4, 129.3, 113.5, 113.1, 58.2, 24.9;
H
3
1
3
3
(
b) Bohm, V. P. W.; Weskamp, T.; Gstottmayr, C. W. K.;
Herrmann, W. A. Angew. Chem., Int. Ed. 2000, 39, 1602;
c) Huang, J.; Nolan, S. P. J. Am. Chem. Soc. 1999, 121,
Anal. Calcd for C14
58.25; H, 2.92.
H
F
O: C, 58.34; H, 3.15. Found: C,
9
5
(
0
1
2-Cyano-5-fluoro-4 -methoxydiphenylmethane: H NMR
9889; (d) Li, G. Y.; Marshall, W. J. Organometallics 2002,
2
1, 590; (e) Li, G. Y. J. Organomet. Chem. 2002, 653, 63;
(199.976 MHz, CDCl
2H), 6.80 (d, 2H), 3.78 (s, 2H), 3.75(s, 3H);
(50.289 MHz, CDCl ) d 167.5, 163.2, 140.1, 135.3, 132.4,
129.3, 115.4, 113.9, 113.1, 110.6, 58.2, 38.8; Anal. Calcd for
12FNO: C, 74.67; H, 5.01; N, 5.81. Found: C, 75.19; H,
4.95; N, 5.55.
2-Trifluoromethyl-4-nitro-4 -methoxydiphenylmethane: H
NMR (199.976 MHz, CDCl ) d 8.31 (s, 1H), 7.67 (d, 1H),
7.23 (d, 2H), 7.05(d, 1H), 6.83 (d, 2H), 3.78 (s, 2H), 3.75(s,
3
) d 7.65(q, 1H), 7.27 (d, 2H), 7.04 (m,
13
(f) Lipshutz, B. H.; Tomioka, T.; Blomgren, P. A.;
Sclafani, J. A. Inorg. Chim. Acta 1999, 296, 164.
C NMR
3
6
. (a) Montgomery, J. Angew. Chem., Int. Ed. 2004, 43, 3890;
(
b) Bedford, R. B.; Cazin, C. S. J.; Holder, D. Coord.
C H
15
Chem. Rev. 2004, 248, 2283; (c) Espinet, P.; Echavarren,
A. M. Angew. Chem., Int. Ed. 2004, 43, 4704.
. Steel, P. G.; Teasdale, C. W. T. Tetrahedron Lett. 2004, 45,
0
1
7
8
9
3
8
977.
. Lipshutz, B. H.; Blomgren, P. A. J. Am. Chem. Soc. 1999,
21, 5819.
1
3
3H); C NMR (50.289 MHz, CDCl
132.4, 129.8, 129.3, 127.7, 124.1, 121.1, 117.4, 113.1, 58.2,
38.9; Anal. Calcd for C15 NO : C, 57.88; H, 3.89; N,
4.50. Found: C, 58.13; H, 3.76; N, 4.49.
3
) d 163.2, 143.7, 139.3,
1
. Lipshutz, B. H.; Sclafani, J. A.; Blomgren, P. A. Tetra-
hedron 2000, 56, 2139.
H
12
F
3
3
1
0. Lipshutz, B. H.; Ueda, H. Angew. Chem., Int. Ed. 2000,
9, 4492.
17. Tasler, S.; Lipshutz, B. H. J. Org. Chem. 2003, 68,
1190.
3