LETTER
Enzymatic Hydrolysis of 2-Acetoxyalkyl Tosylates
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(4) For enzymatic hydrolysis of acyl derivatives of 1,2-diol
strates. Only the glycerol-type substrate ( )-3f bearing the
benzyloxymethyl group (entry 7) showed a moderate
enantioselectivity. In this case, even the slow reactive
enantiomer might be more suitable for the enzyme active
site than those of other substrates. Further investigations
for applying the method and improving the E value for the
hydrolysis of 3f are now in progress.
monotosylates in an aqueous media, see: (a)Hamaguchi,S.;
Ohashi, T.; Watanabe, K. Agric. Biol. Chem. 1986, 50, 375.
(b) Hamaguchi, S.; Ohashi, T.; Watanabe, K. Agric. Biol.
Chem. 1986, 50, 1629. (c) Hamaguchi, S.; Katayama, K.;
Ohashi, T.; Watanabe, K. JP 62158250, 1987.
(d) Hamaguchi, S.; Kobayashi, M.; Katayama, K.; Ohashi,
T.; Watanabe, K. JP 62209049, 1987. (e) Kobayashi, M.;
Hamaguchi, S.; Katayama, K.; Ohashi, T.; Watanabe, K. JP
62212382, 1987. (f) Pederson, R. L.; Liu, K. K.-C.; Rutan, J.
F.; Chen, L.; Wong, C.-H. J. Org. Chem. 1990, 55, 4897.
(g) Chen, C.-S.; Liu, Y.-C.; Marsella, M. J. Chem. Soc.,
Perkin Trans. 1 1990, 2559.
In summary, a simple and efficient approach to produce
optically active 1,2-diol monotosylate derivatives by the
enzyme-mediated hydrolysis has been developed. Fur-
thermore, we observed a unique temperature effect on the
enantioselectivity. This method is applicable for various
compounds, and is expected to be a potentially useful tool
for organic synthesis.
(5) For enzymatic esterification of 1,2-diol monotosylates in
organic solvent, see: (a) Chen, C.-S.; Liu, Y.-C.
Tetrahedron Lett. 1989, 30, 7165. (b) Chênevert, R.;
Gagnon, R. J. Org. Chem. 1993, 58, 1054. (c) Neagu, C.;
Hase, T. Tetrahedron Lett. 1993, 34, 1629. (d) Boaz, N. W.;
Zimmerman, R. L. Tetrahedron: Asymmetry 1994, 5, 153.
(e) Boaz, N. W.; Falling, S. N.; Moore, M. K. Synlett 2005,
1615. (f) For enzymatic hydrolysis in organic solvent, see
ref. 5c. For enzymatic alcoholysis in organic solvent, see ref.
4g and 5a.
Acknowledgment
We thank Material Science Research Center (Meisei University) for
NMR analysis.
(6) For enantioselective decomposition of 1,2-diol
monotosylate by microorganisms, see: Saito, Y.; Nakamura,
T. JP 10057096, 1998.
(7) The substrate ( )-1 was prepared form 1-hexene in 3 steps;
1) OsO4, NMO, acetone–H2O; 2) TsCl, Bu2SnO, Et3N,
CH2Cl2;18 3) Ac2O, pyridine. The details will be reported
separately.
(8) In the screening test, we used the following enzymes: lipase
type II, type VII (Sigma), lipase PS, lipase AY, lipase A,
PLE-A, lipase D-360, lipase AK, lipase D (Amano Enzyme,
Inc.), lipase OF (Meito Sangyo Co., Ltd), lipase (Nagase
ChemteX Corp.), Novozym (NovoNordisk A/S). The
hydrolysis of ( )-1 with lipase type II, lipase type VII, PLE-
A or lipase OF proceeded with low enantioselectivity. The
other enzymes did not catalyze the reaction.
(9) The absolute configurations of 1 and 2 were confirmed by
comparing the obtained optical rotation value with the
reported value: (R)-1, lit.5a [a]D25 +13.4 (CHCl3), 86% ee;
(S)-2, lit.5a [a]D25 +4.2 (CHCl3), 66% ee.
References and Notes
(1) For recent examples, see: (a) Zhu, X.-M.; He, L.-L.; Yang,
G.-L.; Lei, M.; Chen, S.-S.; Yang, J.-S. Synlett 2006, 3510.
(b) Guaragna, A.; De Nisco, M.; Pedatella, S.; Palumbo, G.
Tetrahedron: Asymmetry 2006, 17, 2839. (c) Wang, C.;
Kunts, D. A.; Hamlet, T.; Sim, L.; Rose, D. R.; Pinto, B. M.
Bioorg. Med. Chem. 2006, 14, 8332. (d) Ghosh, A. K.;
Gong, G. Org. Lett. 2007, 9, 1437. (e) Chattopadhyay, A.;
Vichare, P.; Dhotare, B. Tetrahedron Lett. 2007, 48, 2871.
(f) Martynow, J. G.; Jozwik, J.; Szelejewski, W.;
Achmatowicz, O.; Kutner, A.; Wisniewski, K.; Winiarski,
J.; Zegrocka-Stendel, O.; Golebiewski, P. Eur. J. Org.
Chem. 2007, 689. (g) Bedore, M. W.; Chang, S.-K.;
Paquette, L. A. Org. Lett. 2007, 9, 513.
(2) For recent examples, see: (a) El Ashry, E. S. H.; Abdel-
Rahman, A.; Rashed, N.; Awad, L. F.; Rasheed, H. A.
Nucleosides, Nucleotides Nucleic Acids 2006, 25, 299.
(b) Ikura, M.; Nakatani, S.; Yamamoto, S.; Habashita, H.;
Sugiura, T.; Takahashi, K.; Ogawa, K.; Ohno, H.; Nakai, H.;
Toda, M. Bioorg. Med. Chem. 2006, 14, 4241. (c) Koo, B.;
McDonald, F. E. Org. Lett. 2007, 9, 1737.
(10) The ee of 1 was determined by HPLC analysis with
CHIRALCEL AD-H (Daicel Chemical Industries, Ltd.);
eluent: hexane–i-PrOH (90:10); flow rate: 0.5 mL min–1;
tR = 18 (S) and 19.5 (R) min. A similar analysis of 2 was also
performed with CHIRALCEL OD-H; eluent: hexane–
i-PrOH (95:5); flow rate: 0.5 mL min–1; tR = 32 (R) and 35.5
(S) min.
(3) For recent examples, see: (a) Wallner, S. R.; Nestl, B. M.;
Faber, K. Org. Biomol. Chem. 2005, 3, 2652.
(b) Fernandez, C.; Diouf, O.; Moman, E.; Gomez, G.; Fall,
Y. Synthesis 2005, 1701. (c) Masutani, K.; Minowa, T.;
Hagiwara, Y.; Mukaiyama, T. Bull. Chem. Soc. Jpn. 2006,
79, 1106. (d) Miranda, P. O.; Ramirez, M. A.; Martin, V. S.;
Padron, J. I. Org. Lett. 2006, 8, 1633. (e) Sharma, G. V. M.;
Reddy, J. J.; Reddy, K. L. Tetrahedron Lett. 2006, 47, 6531.
(f) Chen, C.-L.; Sparks, S. M.; Martin, S. F. J. Am. Chem.
Soc. 2006, 128, 13696. (g) Mohapatra, D. K.; Ramesh, D.
K.; Giardello, M. A.; Chorghade, M. S.; Gurjar, M. K.;
Grubbs, R. H. Tetrahedron Lett. 2007, 48, 2621.
(h) Chattopadhyay, A.; Vichare, P.; Dhotare, B. Tetrahedron
Lett. 2007, 48, 2871. (i) Fernandez, C.; Gandara, Z.;Gomez,
G.; Covelo, B.; Fall, Y. Tetrahedron Lett. 2007, 48, 2939.
(j) Suhara, Y.; Oka, S.; Kittaka, A.; Takayama, H.; Waku,
K.; Sugiura, T. Bioorg. Med. Chem. 2007, 15, 854.
(11) Chen, C.-S.; Fujimoto, Y.; Girdaukas, G.; Sih, C. J. J. Am.
Chem. Soc. 1982, 104, 7294.
(12) Compound (S)-1: 1H NMR (300 MHz, CDCl3): d = 0.86 (t,
J = 7.0 Hz, 3 H) 1.13–1.34 (m, 4 H), 1.46–1.65 (m, 2 H),
1.98 (s, 3 H), 2.46 (s, 3 H), 4.05 (dd, J1 = 5.5 Hz, J2 = 10.5
Hz, 1 H), 4.10 (dd, J1 = 3.5 Hz, J2 = 10.5 Hz, 1 H), 4.90–5.00
(m, 1 H), 7.35 (d, J = 8.5 Hz, 2 H), 7.79 (d, J = 8.5 Hz, 2 H).
13C NMR (75 MHz, CDCl3): d = 13.7, 20.8, 22.2, 27.0, 30.0,
70.0, 70.9, 127.8, 130.0, 132.7, 145.0, 170.3. IR (neat):
3460, 2957, 2870, 1730, 1597, 1454, 1362, 1177 cm–1. MS
(EI): m/z (%) = 314 (7.2) [M+], 254 (27), 228 (38), 198 (16),
172 (16), 143 (36), 129 (17), 91 (100), 82 (16). HRMS: m/z
[M+] calcd for C15H22O5S: 314.1188; found: 314.1187.
(13) Compound (R)-2: 1H NMR (300 MHz, CDCl3): d = 0.87 (t,
J = 7.0 Hz, 3 H), 1.10–1.53 (m, 6 H), 2.19 (br s, 1 H), 2.45
(s, 3 H), 3.78–3.91 (m, 1 H), 3.84–3.94 (m, 1 H), 4.00–4.08
(m, 1 H), 7.36 (d, J = 8.5 Hz, 2 H), 7.80 (d, J = 8.5 Hz, 2 H).
13C NMR (75 MHz, CDCl3): d = 13.8, 21.5, 22.4, 27.2, 32.2,
Synlett 2008, No. 3, 367–370 © Thieme Stuttgart · New York