2744
S. Sayama, T. Onami
LETTER
Org. Chem. 1995, 60, 2200. (g) Stowell, J. C.; Ham, B. M.;
Esslinger, M. A.; Duplantier, A. J. J. Org. Chem. 1989, 54,
1212. (h) Okimoto, M.; Chiba, T. J. Org. Chem. 1988, 53,
218. (i) Wilson, S. R.; Tofigh, S.; Misra, R. N. J. Org. Chem.
1982, 47, 1360. (j) Stevens, R. V.; Chapman, K. T.; Stubbs,
C. A.; Tam, W. W.; Albizati, K. F. Tetrahedron Lett. 1982,
23, 4647. (k) Nwaukwa, S. O.; Keehn, P. M. Tetrahedron
Lett. 1982, 23, 35. (l) Pinnick, H. W.; Lajis, N. H. J. Org.
Chem. 1978, 43, 371. (m) Sundararaman, P.; Walker, E. C.;
Djerassi, C. Tetrahedron Lett. 1978, 1627. (n) Ogawa, T.;
Matsui, M. J. Am. Chem. Soc. 1976, 98, 1629. (o) Corey, E.
J.; Gilman, N. W.; Ganem, B. E. J. Am. Chem. Soc. 1968, 90,
5616.
to give a mixture of o- and p-bromophenylethylalcohols
without producing dimeric ester. Therefore, the dimeric
esterification of p-bromophenylethylalcohol unaffected
by further bromination was examined. The reaction of p-
bromophenylethylalcohol with PHPB–H2O afforded
dimeric ester in 53% yield. It was suggested that dimeric
esterification of aromatic alcohols progressed favorably
under the conditions which depressed bromination for the
aromatic ring. The polybromination reaction of organic
compounds by perbromide has been known to be sup-
pressed in the presence of pyridine.14 Therefore, the ester-
ification of 2-methyl-2-phenylpropanol was carried out in
the presence of 2.0 molar equivalents of pyridine over 2-
methyl-2-phenylpropanol. Dimeric ester was obtained in
61% yield, which was beyond our expectation.15 As
mentioned above, Tishchenko-like dimeric esterification
of variable aromatic alcohols in contrast with aliphatic
alcohols, has turned out to be particularly difficult with
PHPB–H2O. It is neccessary to study further optimal
esterification methods for converting aromatic alcohols to
dimeric esters in moderate yields.
(4) 4-Methylbenzoic acid was recovered in 88% yield at 2.0
molar equiv of PHPB and 16 molar equiv of ethylene glycol
over 4-methylbenzoic acid in H2O for 14 h.
(5) (a) Saitoh, K.; Shiina, I.; Mukaiyama, T. Chem. Lett. 1998,
679. (b) Brinchi, L.; Germani, R.; Savelli, G. Tetrahedron
Lett. 2003, 44, 6583. (c) Zander, N.; Gerhardt, J.; Frank, R.
Tetrahedron Lett. 2003, 44, 6557. (d) Enholm, E. J.;
Bhardawaj, A. Tetrahedron Lett. 2003, 44, 3763.
(e) Gacem, B.; Jenner, G. Tetrahedron Lett. 2003, 44, 1391.
(f) Pan, W.-B.; Chang, F.-R.; Wei, L.-M.; Wu, M.-J.; Wu,
Y.-C. Tetrahedron Lett. 2003, 44, 331. (g) Jang, D. O.; Cho,
D. H.; Kim, J.-G. Synth. Commun. 2003, 33, 2885.
(h) Karade, N. N.; Shirodkar, S. G.; Potrekar, R. A.; Karade,
H. N. Synth. Commun. 2004, 34, 391.
(6) (a) Reis, M. G.; Faria, A. D.; Amaral, M. C. E.; Marsaioli, A.
J. Tetrahedron Lett. 2003, 44, 8519. (b) Ueki, T.;
Morimoto, Y.; Kinoshita, T. J. Chem. Soc., Chem. Commun.
2001, 1820. (c) Hisamatsu, Y.; Goto, N.; Hasegawa, K.;
Shigemori, H. Tetrahedron Lett. 2003, 44, 5553.
(d) Schulz, T.; Eicher, T. Synthesis 2003, 1253.
Although a variety of oxidizing reagents have been shown
to convert primary alcohols with methanol into methyl
carboxylates by intermolecular esterification and diols
into lactones by intramolecular esterification,16–20 there
are few methods for the synthesis of Tishchenko-like
dimeric esters of primary alcohols without using organic
solvents. Thus, the system PHPB–H2O also provides a
significant alternative method for obtaining Tishchenko-
like dimeric esters of various aliphatic primary alcohols
without using organic solvents.21
(7) The oxidation of 2-ethyl-1,3-hexanediol (18) containing
both secondary and primary hydroxyl groups, was carried
out with 2.0 molar equiv of PHPB over 18 in H2O at r.t. for
75 h. Only the secondary 3-hydroxyl group of 18 was
selectively oxidized to give hydroxyketone 19 in 82% yield
(Table 6, run 6).
References
(8) Typical procedure for the Esterification of
Isobutyraldehyde (4) and Dodecanol:
(1) (a) Larock, R. C. In Comprehensive Organic
Transformation; Wiley-VCH: New York, 1999. (b) Ho, T.-
L. Fiesers’ Reagents for Organic Synthesis, Vol. 1-21;
Wiley: New York, 1967-2003. (c) Naik, S.; Gopinath, R.;
Goswami, M.; Patel, B. K. Org. Biomol. Chem. 2004, 2,
1670. (d) Gopinath, R.; Haque, S. K.; Patel, B. K. J. Org.
Chem. 2002, 67, 5842. (e) Naik, S.; Gopinath, R.; Patel, B.
K. Tetrahedron Lett. 2001, 42, 7679. (f) Gopinath, R.;
Patel, B. K. Org. Lett. 2000, 2, 4177. (g) Bora, U.; Bose, G.;
Chaudhuri, M. K.; Dhar, S. S.; Gopinath, R.; Khan, A. T.;
Patel, B. K. Org. Lett. 2000, 2, 247.
To a solution of PHPB (320 mg, 1.00 mmol) in H2O (8 mL)
were added 4 (36 mg, 0.50 mmol) and dodecanol (93 mg,
0.50 mmol). After stirring for 14 h at r.t., the reaction
mixture was treated with 0.5 M aq Na2S2O3 and extracted
with EtOAc. The organic layer was washed with 0.5 M aq
Na2S2O3, successively sat. aq NaCl, and dried over MgSO4.
After removal of the solvent in vacuo, the residue was
purified by column chromatography on silica gel (Wakogel
C-200) with CCl4 and CHCl3 (3:1 v/v). Ester 4a (109 mg,
0.42 mmol) was obtained in 84% yield.
(2) (a) Dessolin, J.; Biot, C.; Davioud-Charvet, E. J. Org. Chem.
2001, 66, 5616. (b) Chaudhuri, M. K.; Khan, A. T.; Patel, B.
K.; Dey, D.; Kharmawophlang, W.; Lakshmiprabha, T. R.;
Mandal, G. C. Tetrahedron Lett. 1998, 39, 8163.
(9) Yunker, M. B.; Fraser-Reid, B. J. Chem. Soc., Chem.
Commun. 1975, 61.
(10) Guo, Z.; Padmakumar, R.; Hollingsworth, R. I.;
Radhakrishnan, K. V.; Nandakumar, M. V.; Fraser-Reid, B.
Synlett 2003, 1067.
(11) Ermolenko, L.; Sasaki, N. A.; Potier, P. Synlett 2001, 1565.
(12) Kageyama, T.; Ueno, Y.; Okawara, M. Synthesis 1983, 815.
(13) Masuyama, Y.; Takahashi, M.; Kurusu, Y. Tetrahedron Lett.
1984, 25, 4417.
(14) Dauben, W. G.; Warshawsky, A. M. Synth. Commun. 1988,
18, 1323.
(15) b-Phenylethylalcohol was recovered unchanged in 90%
yield at a molar ratio of b-phenylethylalcohol, PHPB,
pyridine (1:2:2) in H2O for 18 h.
(16) Tanaka, H.; Kawakami, Y.; Goto, K.; Kuroboshi, M.
Tetrahedron Lett. 2001, 42, 445.
(c) Collado, I. G.; Galan, R. H.; Massanet, G. M.; Alonso, M.
S. Tetrahedron 1994, 50, 6433. (d) Baraldi, P. G.;
Bazzanini, R.; Manfredini, S.; Simoni, D.; Robins, M. J.
Tetrahedron Lett. 1993, 34, 3177. (e) Reeves, W. P.; King,
R. M. II Synth. Commun. 1993, 23, 855. (f) Husstedt, U.;
Schafer, H. J. Synthesis 1979, 966.
(3) (a) Qian, G.; Zhao, R.; Ji, D.; Lu, G.; Qi, Y.; Suo, J. Chem.
Lett. 2004, 33, 834. (b) Gopinath, R.; Barkakaty, B.;
Talukdar, B.; Patel, B. K. J. Org. Chem. 2003, 68, 2944.
(c) Sharghi, H.; Sarvari, M. H. J. Org. Chem. 2003, 68,
4096. (d) Gopinath, R.; Patel, B. K. Org. Lett. 2000, 2, 577.
(e) Espeson, J. H.; Zhu, Z.; Zauche, T. H. J. Org. Chem.
1999, 64, 1191. (f) Gregg, P. J.; Olsson, L.; Oscarson, S. J.
Synlett 2004, No. 15, 2739–2745 © Thieme Stuttgart · New York