RESEARCH FRONT
Malonic Acid Monoesterification by Boric Acid
823
Procedure B
[5] J. Jammot, R. Pascal, A. Commeyras, J. Chem. Soc., Perkin Trans. 2
1990, 157. doi:10.1039/P29900000157
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doi:10.1021/JO025876Y
Malonic acid (500 mg, 4.81 mmol) was stirred with boric acid
(15 mg, 0.24 mmol) and 2-ethylbutan-1-ol (430 mg, 4.81 mmol)
in acetonitrile and stirred at 60◦C for 24 h. Flash column
chromatography furnished 7 in slightly lower yield (450 mg,
2.39 mmol, 50%).
δH (300 MHz, CDCl3) 0.89 (t, 3H, J 7.2), 1.36 (app. qn, 4H,
J 7.2), 1.55 (app. sept, 1H, J 6.0), 3.44 (s, 2H), 4.10 (d, 2H,
J 6.0). δC (75 MHz, CDCl3) 10.9, 40.1, 41.0, 67.9, 74.9, 166.9,
172.0. (HRMS Found: 211.09473. Calc. for C6H6O4 + Na+:
211.09408.)
(b) J. Z. Zhao, T. M. Fyles, T. D. James, Angew. Chem. Int. Ed. 2004,
43, 3461. doi:10.1002/ANIE.200454033
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IC50158A054
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3-Oxo-3-(prop-2-ynyloxy)propanoic Acid (9)
Procedure A
[8] T. Maki, K. Ishihara, H. Yamamoto, Org. Lett. 2005, 7, 5047.
doi:10.1021/OL052061D
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doi:10.1021/JA00291A042
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[10] (a) C.-T. Chen, Y. S. Munot, J. Org. Chem. 2005, 70, 8625.
doi:10.1021/JO051337S
Propargyl alcohol (2.1 mL) and malonic acid (500 mg,
4.81 mmol) were combined with boric acid (59 mg, 0.96 mmol)
and stirred at 70◦C for 24 h. Excess propargyl alcohol was
removed by reduced pressure and flash column chromato-
graphy (1/9, methanol/dichloromethane) was used to isolate 9
as a colourless oil (520 mg, 3.66 mmol, 76%).
(b) H. N. Roy, A. H. Al Mamun, Synth. Commun. 2006, 2975.
doi:10.1080/00397910600773759
(c) For a recent summary of chemselective esterifications, see:
M. Nahmany, A. Melman, Org. Biomol. Chem. 2004, 2, 1563.
doi:10.1039/B403161J
Procedure B
Malonic acid (500 mg, 4.81 mmol) and propargyl alcohol
(269 mg, 4.81 mmol) were combined and heated at 70◦C for 24 h
stirring in acetonitrile solvent. Acetonitrile was then removed by
reduced pressure before flash column chromatography was used
to provide 9 as a colourless oil (463 mg, 3.26 mmol, 68%).
δH (300 MHz, CDCl3) 2.50 (t, 1H, J 2.4, CH), 3.41 (s, 2H,
CH2), 4.65 (s, 2H, J 2.4, OCH2), 10.6–10.9 (br m, 1H, CO2H). δC
(75 MHz, CDCl3) 40.7, 53.1, 75.9, 165.9, 171.2. (HRMS Found:
165.01594. Calc. for C6H6O4 + Na+: 165.01583.)
[11] H. Junek, E. Ziegler, U. Herzog, H. Kroboth, Synthesis 1976, 322.
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30, 3073. doi:10.1016/S0040-4039(00)99406-1
[13] J. De La Zerda, G. Barak, Y. Sasson, Tetrahedron 1989, 45, 1533.
doi:10.1016/0040-4020(89)80151-6
[14] T. Maki, I. Kazuaki, H. Yamamoto, Synlett 2004, 1355.
[15] R. H.Tale,A. D. Sagar, H. D. Santan, R. N.Adude, Synlett 2006, 0415.
doi:10.1055/S-2006-932454
[16] (a) D. Rehn, I. Ugi, J. Chem. Res., Synop. 1977, 119.
(b) A. Padwa, D. C. Dean, D. J. Fairfax, S. L. Xu, J. Org. Chem. 1993,
58, 4646. doi:10.1021/JO00069A030
[17] (a) W.-J. Chen, D. Y. Lee, R. N. Armstrong, J. Org. Chem. 1986, 51,
2848. doi:10.1021/JO00364A055
Acknowledgement
We thank the Institute for Glycomics and Griffith University for financial
support. We are also grateful to Dr Sally-Ann Poulsen and Mr. Hoan The Vu
(Eskitis Institute for Cell and Molecular Therapies, Griffith University) for
high-resolution mass spectrometry data.
(b) Y. Ryu, A. I. Scott, Tetrahedron Lett. 2003, 44, 7499.
doi:10.1016/J.TETLET.2003.08.014
[18] B. Devadas,T. B. Lu,A. Katoh, N. S. Kishore,A. C. Wade, P. P. Mehta,
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AID-HLCA678>3.0.CO;2-Y
(b) C.-N. Xia, W.-X. Hu, J. Chem. Res. 2005, 5, 332.
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doi:10.1016/S0040-4039(00)98555-1
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