Tatsushi Imahori et al.
COMMUNICATIONS
saturated aqueous NH4Cl was added to the mixture, and the
mixture was extracted with CHCl3. The organic layer was dried
over MgSO4 and the solvent was removed under reduced pres-
sure. The residue was purified by SiO2 column chromatography
using n-hexane as an eluent to give 1-methoxy-1, 2-diphenyl-
Dohle, P. Knochel, Angew., Chem. Int. Ed. 2000, 39,
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1
ethane as a mixture of E- and Z-isomers (50:50). H NMR
(300 MHz, CDCl3, TMS): d (Z-isomer)¼3.70 (s, 3H), 6.10 (s,
1H), 7.21–7.73 (m, 10H); d (E-isomer)¼3.81 (s, 3H), 5.83 (s,
1H), 6.95–7.13 (m, 5H); IR (neat): n¼3022, 2829, 1636, 1600,
1235, 1198, 1119, 729, 693 cmꢀ1; MS: m/z¼210 (Mþ).
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Typical Procedure for the Reaction of
Phenylacetylene with Acetone in the Presence of t-Bu-
P4 Base
Under an argon atmosphere, a mixture of phenylacetylene
(31.1 mg, 0.3 mmol), acetone (0.04 mL, 0.5 mmol), t-Bu-P4
base (1 M solution in hexane, 0.1 mL, 0.1 mmol), and DMSO
(0.5 mL) was stirred at 1208C for 24 h. After the reaction, satu-
rated aqueous NH4Cl was added to the mixture, and the mix-
ture was extracted with CHCl3. The organic layer was dried
over MgSO4 and the solvent was removed under reduced pres-
sure. The residue was purified by SiO2 column chromatography
using hexane-AcOEt (10:1) as an eluent to give 2-methyl-4-
phenyl-but-3-yn-2-ol. 1H NMR (300 MHz, CDCl3, TMS): d¼
1.59 (s, 1H), 1.63 (s, 6H), 7.26–7.31 (m, 3H), 7.40–7.44 (m,
2H); IR (neat): n¼3350, 2981, 1490, 1160, 960, 754, 689 cmꢀ1
;
MS: m/z¼160 (Mþ).
[9] a) M. Nishiura, N. Hou, Y. Wakatsuki, T. Yamaki, T.
Miyamoto, J. Am. Chem. Soc. 2003, 125, 1184–1185;
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Acknowledgements
This work was partially supported by Grant-in-Aid for Scientif-
ic Research on Priority Areas (No. 15036208, “Reaction Control
of Dynamic Complexes”) from Ministry of Education, Culture,
Sports, Science and Technology, Japan. JSPS Research Fellow-
ships for Young Scientists (No. 07175) to T. Imahori is also
gratefully acknowledged.
[10] a) X. Li, G. Lu, W. H. Kwok, A. S. C. Chan, J. Am.
Chem. Soc. 2002, 124, 12636; b) C. Wei, C.-J. Li, Green
Chemistry 2002, 4, 39.
[11] L. Brandsma, Preparative Acetylenic Chemistry, 2nd edn.,
Elsevier, Amsterdam, 1988.
References and Notes
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1463.
[13] Recently a catalytic alkynylation of carbonyl compounds
using quaternary ammonium hydroxide base was report-
ed: T. Ishikawa, T. Mizuta, K. Hagiwara, T. Aikawa, T.
Kudo, S. Saito, J. Org. Chem. 2003, 68, 3702.
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1092
ꢀ 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
Adv. Synth. Catal. 2004, 346, 1090–1092