Y. M. A. Yamada, Y. Uozumi / Tetrahedron 63 (2007) 8492–8498
8497
4.4. General procedure for a-alkylation of the ketones
4 with the primary alcohols 5 in the presence of nano-
Pd-V 3 and Ba(OH)2$H2O
Culture, Sports, Science and Technology, Japan) and man-
aged by the Institute for Molecular Science.
References and notes
To a mixture of nano-Pd-V 3 (10 mg) and Ba(OH)2$H2O
(63 mg) was added water (42 mL), and the suspension was
mixed by a vortex mixer for 1 min at 25 ꢀC. Compounds 4
(0.334 mmol) and 5 (0.668 mmol) were added to the reac-
tion mixture, which was stirred at 100 ꢀC for 24 h. For the
reactions shown in Table 2, entries 4–12, the mixture was
purified by column chromatography (eluant: EtOAc/hexane)
to give 6. For the reactions shown in Table 2, entries 1–3,
EtOAc (8 mL) was added to the reaction mixture, which
was then centrifuged at 4000 rpm for 5 min. EtOAc layer
was decanted and analyzed by GC to determine the GC yield
of 6a. To the residue was added water (8 mL), followed by
centrifugation at 4000 rpm for 5 min and decantation of
the aqueous layer to give a black powder that was dried at
5 Pa for 12 h and used for the next reaction as a reusable
catalyst.
1. (a) Hirai, T.; Toshima, N. Polymeric Materials Encyclopedia;
Salamone, J. S., Ed.; CRC: Boca Raton, FL, 1996; Vol. 2/c,
p 1, 1310; (b) Bradley, J. S. Clusters and Colloids; Schmid,
G., Ed.; VCH: Weinheim, 1994.
2. (a) Uozumi, Y.; Nakao, R. Angew. Chem., Int. Ed. 2003, 42,
194; (b) Nakao, R.; Rhee, H.; Uozumi, Y. Org. Lett. 2005, 7,
163; (c) Yamada, Y. M. A.; Arakawa, T.; Hocke, H.; Uozumi,
Y. Angew. Chem., Int. Ed. 2007, 46, 704; (d) Uozumi, Y.;
Nakao, R.; Rhee, H. J. Organomet. Chem. 2007, 692, 420.
3. For reviews, see: (a) Mallat, T.; Baiker, A. Chem. Rev. 2004,
104, 3037; (b) Zhan, B.-Z.; Thompson, A. Tetrahedron 2004,
60, 2917; (c) Corain, B.; Kralik, M. J. Mol. Catal. A: Chem.
2001, 173, 99; For recent improvements, see: (d) Okamoto,
K.; Akiyama, R.; Yoshida, H.; Yoshida, T.; Kobayashi, S.
J. Am. Chem. Soc. 2005, 127, 2125; (e) Bedford, R. B.;
Singh, U. G.; Walton, R. I.; Williams, R. T.; Davis, S. A.
Chem. Mater. 2005, 17, 701; (f) Centomo, P.; Zecca, M.;
Lora, S.; Vitulli, G.; Caporusso, A. M.; Tropeano, M. L.;
Milone, C.; Galvagno, S.; Corain, B. J. Catal. 2005, 229,
283; (g) Wu, H.; Zhang, Q.; Wang, Y. Adv. Synth. Catal.
2005, 347, 1356; (h) Karimi, B.; Zamani, A.; Clark, J. H.
Organometallics 2005, 24, 4695; (i) Shi, F.; Zhang, Q.; Ma,
Y.; He, Y.; Deng, Y. J. Am. Chem. Soc. 2005, 127, 4182; (j)
Kang, R.; Ouyang, X.; Han, J.; Zhen, X. J. Mol. Catal. A:
Chem. 2001, 175, 153; (k) Zecca, M.; Fisera, R.; Palma, G.;
Lora, S.; Hronec, M.; Kralik, M. Chem.—Eur. J 2000, 6,
1980 and references cited therein.
4.4.1. 1-Cyclohexyl-3-(4-methoxyphenyl)propan-1-one
1
(6g). H NMR (500 MHz, CDCl3) d 7.09 (d, J¼8.5 Hz,
2H), 6.81 (d, J¼8.5 Hz, 2H), 3.78 (s, 3H), 2.82 (t,
J¼7.6 Hz, 2H), 2.71 (t, J¼7.6 Hz, 2H), 2.27–2.33 (m, 1H),
1.58–1.81 (m, 5H), 1.16–1.34 (m, 5H); 13C NMR
(126 MHz, CDCl3) d 213.3, 157.9, 133.5, 129.2, 113.8,
55.2, 51.0, 42.8, 28.8, 28.4, 25.8, 25.6; IR (ATR) n 2926,
2853, 1704, 1611, 1512, 1466, 1448, 1230, 1239, 1177,
1090, 1035, 890, 827, 630 cmꢁ1; MS(EI(+)) 246 (M+), 163
121 (a base peak); HRMS (ESI(+)) calcd for C16H22O2Na
(M+Na+) 269.1518, found 269.1526.
4.5. General procedure for ring-opening alkylation of
the cyclic diketones 7 with the primary alcohols 5 in the
presence of nano-Pd-V 3 and Sr(OH)2$8H2O
4. A review, see: Yamada, Y. M. A. Chem. Pharm. Bull. 2005,
53, 723.
5. Examples, see: (a) Yamada, Y. M. A.; Ichinohe, M.; Takahashi,
H.; Ikegami, S. Org. Lett. 2001, 3, 1837; (b) Yamada, Y. M. A.;
Ichinohe, M.; Takahashi, H.; Ikegami, S. Tetrahedron Lett.
2002, 43, 3431; (c) Yamada, Y. M. A.; Takeda, K.;
Takahashi, H.; Ikegami, S. Org. Lett. 2002, 4, 3371; (d)
Yamada, Y. M. A.; Tabata, H.; Takahashi, H.; Ikegami, S.
Synlett 2002, 2031; (e) Yamada, Y. M. A.; Takeda, K.;
Takahashi, H.; Ikegami, S. Tetrahedron Lett. 2003, 44, 2379;
(f) Yamada, Y. M. A.; Takeda, K.; Takahashi, H.; Ikegami, S.
J. Org. Chem. 2003, 68, 7733; (g) Yamada, Y. M. A.; Tabata,
H.; Ichinohe, M.; Takahashi, H.; Ikegami, S. Tetrahedron
2004, 60, 4087; (h) Yamada, Y. M. A.; Takeda, K.;
Takahashi, H.; Ikegami, S. Tetrahedron 2004, 60, 4097; (i)
Hamamoto, H.; Suzuki, Y.; Yamada, Y. M. A.; Tabata, H.;
Takahashi, H.; Ikegami, S. Angew. Chem., Int. Ed. 2005, 44,
4536; (j) Yamada, Y. M. A.; Maeda, Y.; Uozumi, Y. Org.
Lett. 2006, 8, 4259.
To a mixture of nano-Pd-V 3 (10 mg) and Sr(OH)2$8H2O
(89 mg) was added water (42 mL), and the resulting suspen-
sion was mixed by a vortex mixer for 1 min at 25 ꢀC. Com-
pounds 7 (0.334 mmol) and 5 (0.668 mmol) were added
to the suspension and the mixture was stirred at 80 ꢀC for
24 h. After being cooled, 1 M aqueous HCl (3 mL) and
EtOAc (5 mL) were added to the reaction mixture, the
organic layer was separated, and the aqueous layer was ex-
tracted with EtOAc (3ꢂ10 mL). The organic layer combined
was washed with brine, dried over Na2SO4, and concen-
trated. The residue was purified by silica gel column
chromatography (eluant: EtOAc/hexane) to give 8.
Acknowledgements
6. A Preliminary result on a-alkylation of ketones was shown,
see: Yamada, Y. M. A.; Uozumi, Y. Org. Lett. 2006, 8, 1375.
7. (a) Bhowmik, P. K.; Han, H.; Cebe, J. J.; Burchett, R. A.;
Sarker, A. M. J. Polym. Sci., Part A: Polym. Chem. 2002, 40,
659; (b) Moore, J. S.; Stupp, S. I. Macromolecule 1986, 19,
1815.
8. Homogeneous catalysis; (a) Cho, C. S.; Kim, B. T.; Kim, T.-J.;
Shim, S. C. Tetrahedron Lett. 2002, 43, 7987; (b) Taguchi, K.;
Nakagawa, H.; Hirabayashi, T.; Sakaguchi, S.; Ishii, Y. J. Am.
This work was supported by the CREST program, sponsored
by the JST. We also thank the JSPS (Grant-in-Aid for Scien-
tific Research, no.15205015 and no. 16790025), the MEXT
(Scientific Research on Priority Areas, no. 460 and 420), and
the Uehara Memorial Foundation for partial financial sup-
port of this work. We are thankful to Ms. Michiko Nakano
(IMS) for the 920 MHz solid-phase NMR measurements
(JEOL JNM-ECA920) and to Dr. Satoru Nakao (IMS) for his
help in measuring SEM, which are supported by the Nano-
technology Support Project (The Ministry of Education,
ꢀ
Chem. Soc. 2004, 126, 72; (c) Martınez, R.; Brand, G. J.;
Ramon, D. J.; Yus, M. Tetrahedron Lett. 2005, 46, 3683;
ꢀ