6512
A. S. Demir et al. / Tetrahedron 60 (2004) 6509–6512
drying the collected organic phase over MgSO , removal of
4
the solvent under reduced pressure gave the crude product,
which was then purified by flash column chromatography
(f) Larsen, S. D.; Grieco, P. A.; Fobare, W. F. J. Am. Chem.
Soc. 1986, 108, 3512–3513.
2. (a) Snider, B. B.; Rodini, D. J.; Kirk, T. C.; Cordova, R. J.
J. Am. Chem. Soc. 1982, 104, 555–563. (b) Snider, B. B. In
Selectivities in Lewis Acid Promoted Reactions; Schinzer, D.,
Ed.; Kluwer: London, 1989; pp 147–167. (c) Maruoka, K.;
Conception, A. B.; Hirayama, N.; Yamamoto, H. J. Am. Chem.
Soc. 1990, 112, 7422–7423. (d) Maruoka, K.; Concepcion,
A. B.; Murase, N.; Oishi, M.; Yamamoto, H. J. Am. Chem.
Soc. 1993, 115, 3943–3949.
(
compound 2-hydroxy-1-(4-hydroxyphenyl)ethan-1-one. Mp
EtOAc:hexane 1:3) to give 135 mg (89%) of the desired
1
3
1
1
65–167 (Lit. 165–167); H NMR (CDCl ): d 4.03 (br
3
s,OH, 1H), 4.67 (s, 2H), 6.79 (d, J¼8.4 Hz, 2H), 7.72 (d,
J¼8.4 Hz, 2H).
4
.2. General procedure for the synthesis of (S)-benzoins
and 2-hydroxy-1-arylethan-1-one from rac. benzoins:
representative example: (S)-2-hydroxy-1,2-bis(4-methyl-
phenyl)ethan-1-one ((S)-3e) and 2-hydroxy-1-(4-methyl-
phenyl)-1-one (2b)
3. (a) Mukaiyama, T.; Banno, K.; Narasaka, K. J. Am. Chem.
Soc. 1974, 96, 7503–7509. (b) Murata, S.; Suzuki, M.; Noyori,
R. Tetrahedron Lett. 1980, 21, 2527–2528.
4. Kobayashi, S.; Hachiya, I. J. Org. Chem. 1994, 59, 3590–3596.
5
. (a) Sch o¨ rken, U.; Sprenger, G. A. Biochim. Biophys. Acta
1998, 1385, 229–243. (b) Turner, N. J. Curr. Opin.
Biotechnol. 2000, 11, 527–531. (c) Ward, O. P.; Singh, A.
Curr. Opin. Biotechnol. 2000, 11, 520–526. (d) Ward, O. P. In
Stereoselective Biocatalysis; Patel, R. N., Ed.; Marcel Dekker:
New York, 2000; p 487. (e) Breuer, M.; Hauer, B. Curr. Opin.
Biotech. 2003, 14, 570–576.
Rac-3e (240 mg, 1 mmol) was dissolved in a mixture of
DMSO (20 mL) and potassium phosphate buffer (80 mL,
5
0 mM, pH 7.0, containing MgSO (2.5 mM) and ThDP
4
(
0.15 mM)). To this solution was added 4 mmol formalde-
hyde solution. After the addition of BAL (40 U), the
reaction was allowed to stand at room temperature. After
2
4 h, 20–50 U of BAL and 4 mmol of formaldehyde
6. (a) White, M. J.; Leeper, F. J. J. Org. Chem. 2001, 66,
5124–5131. (b) Teles, J. H.; Melder, J. P.; Ebel, K.; Schneider,
R.; Harder, W.; Brode, S.; Enders, D.; Breuer, K.; Raabe, G.
Helv. Chim. Acta 1996, 79, 61–83. (c) Enders, D.; Breuer, K.;
Teles, J. H. Helv. Chim. Acta 1996, 79, 1217–1221. (d) Enders,
D.; Kallfass, U. Angew. Chem., Int. Ed. 2002, 41, 1743–1744.
7. Matsumoto, T.; Ohishi, M.; Inoue, S. J. Org. Chem. 1985, 50,
603–606.
solution were added. This was repeated every 24 h until no
more (R)-benzoin was observed. After 6 days, only (S)-3e
and 2b were detected (HPLC). The mixture was extracted
with dichloromethane (250 mL) and the organic layer
washed with water (25 mL) and brine (25 mL) and dried
over MgSO . Evaporation of the solvent and separation
4
of the crude products by column chromatography afforded
(
S)-3e and 2b.
8. (a) Corey, E. J.; Link, J. O. Tetrahedron Lett. 1990, 31,
6
01–604. (b) Corey, E. J.; Link, J. O. J. Org. Chem. 1991, 56,
4
.2.1. Compound (S)-3e. Colorless solid; yield: 93 mg,
1
442–444. (c) Ramachandran, P. V.; Gong, B.; Brown, H. C.
Chirality 1995, 7, 103–110. (d) Elks, J.; Ganelli, C. R.
Dictionary of Drugs; Chapman and Hall, 1990; p 1160.
(e) Taggart, P.; Sutton, P.; Donaldson, R. Clin. Sci. 1985, 69,
631–636. (f) Wei, Z.-L.; Li, Z.-Y.; Lin, G.-Q. Tetrahedron
1998, 54, 13059–13072.
5
20
D
3
9%; mp 88 8C [Lit. , mp 89 8C]; [a] ¼þ148.2 (c 0.8,
1
CH OH); H NMR (400 MHz, CDCl ): d¼7.83 (d, J¼
3
3
8
5
3
.1 Hz, 2H), 7.18-7.22 (m, 4H), 7.16 (d, J¼8.1 Hz, 2H),
.88 (d, J¼5.8 Hz, 1H), 4.52 (d, J¼5.8 Hz, 1H), 2.36 (s,
H), 2.30 (s, 3H).
9
. (a) Gonz a´ les, B.; Vicu n˜ a, R. J. Bacteriol. 1989, 2401–2405.
(b) Hinrichsen, P.; G o´ mez, I.; Vicu n˜ a, R. Gene 1994, 144,
137–138. (c) Demir, A. S.; Pohl, M.; Janzen, E.; M u¨ ller, M.
J. Chem. Soc., Perkin Trans. 1 2001, 633–635. (d) Janzen,
E. Dissertation, Heinrich-Heine Universitaet D u¨ sseldorf,
4
mp 84 8C [Lit. , mp 83 8C]; H NMR (400 MHz, CDCl ):
.2.2. Compound 2b. Yellow solid; yield: 129 mg, 43%;
1
0
1
3
d¼7.83–7.81 (m, 2H), 7.32–7.28 (m, 2H), 4.86 (s, 2H),
3
.52 (br s, 1H), 2.43 (s, 3H).
¨
002. (e) Demir, A. S.; Sesenoglu, O.; Eren, E.; Hosrik, B.;
2
Pohl, M.; Janzen, E.; Kolter, D.; Feldmann, R.; D u¨ nkelmann,
P.; M u¨ ller, M. Adv. Synth. Catal. 2002, 344, 96–103.
Acknowledgements
(
f) D u¨ nkelmann, P.; Kolter-Jung, D.; Nitsche, A.; Demir,
A. S.; Siegert, P.; Lingen, B.; Baumann, M.; Pohl, M.; M u¨ ller,
Financial support from Middle East Technical University
BAP-2003), the Scientific and Technical Research Council
of Turkey (TUBITAK), the Turkish Academy of Science
M. J. Am. Chem. Soc. 2002, 124, 12084–12085. (g) Demir,
¨
A. S.; S¸ e s¸ enoglu, O.; D u¨ nkelmann, P.; M u¨ ller, M. Org. Lett.
(
¨
2
2
003, 5, 2047–2050. (h) Demir, A. S.; Reis, O. Tetrahedron
004, 60, 3803–3811.
¨
(
TUBA), the Turkish State Planning Organization (DPT).
We would like to thank Dr. Bettina Lingen and Dr. Michael
M u¨ ller, Research Center J u¨ lich-Germany for BAL Gene.
1
1
0. Yoshikawa, N.; Suzuki, T.; Shibasaki, M. J. Org. Chem. 2002,
7, 2556–2565.
1. Voneuw, J.; Neher, R.; Reichstein, T.; Tait, S. A. S.; Tait, J. F.;
6
Wettstein, A. Helv. Chim. Acta 1959, 42, 1817–1829.
12. Judenfind, L.; Reid, E. E. J. Am. Chem. Soc. 1920, 42,
043–1055.
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