J. L. Princival et al. / Tetrahedron Letters 50 (2009) 6368–6371
6371
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4215; (h) Soorukram, D.; Knochel, P. Org. Lett. 2004, 6, 2409; (i) Nájera, C.;
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2.3 mol Lꢀ1) was added. After 5 min freshly prepared THF solution of ZnCl2
(1 mL, 1 mmol, 1 mol Lꢀ1) was added and the mixture was allowed to warm up
to ꢀ10 °C. The mixture was re-cooled to ꢀ78 °C and methyllithium (1.0 mL,
1 mmol, 1 mol Lꢀ1) was added. The mixture was allowed to warm up to 0 °C.
Then freshly distilled benzoyl chloride (6) was added (1 equiv) and the reaction
mixture was stirred for 2 h, poured into aqueous ammonium chloride solution
(2 mL), extracted with ether, and the ether layer was washed with water, dried
over MgSO4, evaporated and the residue was purified by silica gel (230–
400 mesh) chromatography using ethyl acetate/hexane (1:1) to afford 125 mg
of 7. Oil; yield (70%); CAS NR 27927-59-9. 1H NMR (200 MHz; CDCl3) d 1.24
(3H, d, J = 6.1 Hz), 1.77–2.03 (2H, m), 2.99 (1H, s), 3.12 (2H, t, J = 7.0 Hz), 3.89
(1H, sext, J = 6.1 Hz), 7.40–8.00 (5H, m). 13C NMR (50 MHz; CDCl3) d 23.5; 32.9;
34.7; 67.1; 127.9; 128.4; 132.9; 136.6; 200.8. IR (film) cmꢀ1 3420, 3062, 2967,
2929, 1682, 1597, 1449, 1278, 1208, 1128, 1075, 743, 691. MS m/z (rel int.) 160
2. (a) Metzger, A.; Schade, M. A.; Knochel, P. Org. Lett. 2008, 10, 1107; (b) Kneisel,
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4. (a) Klein, R.; Gowley, R. E. J. Am. Chem. Soc. 2007, 129, 4126. and references cited
therein; (b) Lautens, M.; Delanghe, P. H. M.; Goh, J. B.; Zhang, C. H. J. Org. Chem.
1995, 60, 4213. and references cited therein.
5. (a) Petragnani, N.; Stefani, H. A. Tetrahedron 2005, 61, 1613; (b) Comasseto, J.
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Elem. 1992, 67, 83.
6. (a) Comasseto, J. V.; Gariani, R. A. Tetrahedron 2009, 65, 8447; (b) Bassora, B. K.;
Da Costa, C. E.; Gariani, R. A.; Comasseto, J. V.; Dos Santos, A. A. Tetrahedron Lett.
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(60), 115 (68), 105 (100), 77 (65), 50 (60), 43 (36). ½a D24
ꢁ
+12.8 (c 1.4, CHCl3); 99%
ee.
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11. General procedure for the cuprate preparation/capture: (R,S)-4-Hydroxy-1-
phenylpentan-1-one (7): A solution of the (R,S)-(1a) (520 mg, 2 mmol) in THF
(10 mL) was cooled to ꢀ78 °C, and n-butyllithium (1.74 mL, 4 mmol,
2.3 mol Lꢀ1
) was added. After 5 min this solution was transferred via a
cannula to a THF (5 mL) and CuCN (0,179 g, 2 mmol) suspension. The resulting
suspension was stirred until a clear, light yellow solution was formed (1 h at
ꢀ78 °C). This solution was then transferred via a cannula to another flask
containing benzoyl chloride (0.28 g, 2 mmol) in THF (4 mL). The resulting
mixture was stirred at ꢀ78 °C for 30 min, warmed to room temperature, and
then diluted with ammonium hydroxide/ammonium chloride solution (10%,
5 mL) and diethyl ether (5 mL). The mixture was maintained under vigorous
stirring for 30 min and the phases were separated. The organic phase was
washed with brine (2 ꢂ 3 mL) and the aqueous phase was extracted with ethyl
acetate (5 mL). The combined organic phases were dried over magnesium
sulfate, filtered, and the solvent was removed under reduced pressure. The
resulting residue was purified by CC over silica gel, eluting with ethyl acetate/
hexane (1:1) giving 116 mg of 7 (65%) as an analytically pure material. The
spectral data are identical to those of the compound obtained above.
7. Dos Santos, A. A.; Da Costa, C. E.; Princival, J. L.; Comasseto, J. V. Tetrahedron:
Asymmetry 2006, 17, 2252.
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Miyoshik, T.; Sakamoto, T.; Kondo, Y.; Morokuma, K. J. Am. Chem. Soc. 2008, 130,
472; (b) Uchiyama, M.; Nakamura, S.; Ohwada, T.; Nakamura, M.; Nakamura, E.
J. Am. Chem. Soc. 2004, 126, 10897; (c) Uchiyama, M.; Kameda, M.; Mishima, O.;
Yokoyama, N.; Koike, M.; Kondo, Y.; Sakamoto, T. J. Am. Chem. Soc. 1998, 120,
4934.
9. General procedure for the hetero zincate 8a preparation/capture: (S)-4-Hydroxy-1-
phenylpentan-1-one (7): A solution of the (S)-(1a) (520 mg, 2 mmol) in THF
(10 mL) was cooled to ꢀ78 °C and n-butyllithium (1.74 mL, 4 mmol,