A Synthetic Study for Optically Active 3-Hydroxy-2-methylpropanoic Acid Derivatives via Chemical Asymmetric Decarboxylation[1]

Sang Uk Ryu; Young Gyu Kim

Journal of Industrial and Engineering Chemistry, Vol.4, No.1, 50-57, March, 1998

Sang Uk Ryu, and Young Gyu Kim

Department of Chemical Technology, Seoul National University, Seoul 151-742, Korea

3-Hydroxy-2-methylpropanoic acid (β-hydroxyisobutyric acid, HIBA) and its derivatives are both academically and industrially important four-carbon chiral synthons that have one stereogenic center and two different functional groups at both ends of the molecule. Representative application examples are the synthesis of polypropionate natural products of biological and pharmaceutical importance and the preparation of captopril, a billion-dollar seller antihypertensive in 1993. Chemical asymmetric decarboxylation was selected for the preparation of enantiomerically pure HIBA and its derivatives as well as for the developed process to be industrially competent. The required intermediates, 2-hydroxymethyl-2-methylmalonic acid (4) and its mono-ethyl ester 12, were found out to be unstable under acidic or basic conditions, but could be prepared effectively by hydrogenolysis of their benzyl esters under neutral conditions. The overall yield was 86% for 4 in three steps and 77% for 12 in four steps. Although the asymmetric decarboxylation of 4 was not promising, it was successful with 12 to give optically active HIBA product. The chiral catalyst used here was the cinchona alkaloids that consist of two sets of families being pseudoenantiomeric to each other. The asymmetric induction was very low (2~5% ee) with a catalytic amount of the chiral amines but the sense of asymmetric induction was consistent in the same family. Improved enantioselectivities up to 18% ee were realized by use of excess chiral amines although the absolute ee values were not satisfactory. The enhanced ee values were resulted from replacing the proton of an achiral environment with one of the chiral amine salt. This process was flexible enough to produce either enantiomer by simply changing the chiral amine family.

[References]

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[Related Articles]

[1] Presented in part at the Fall '97 Conference of the Korean Society of Industrial and Engineering Chemistry, Suwon, Kyonggi-Do, October 31 ~ Novamber, 1, No. 1PB-24 (1997)

[2] Paterson I, McLeod MD, Tetrahedron Lett., 38, 4183 (1997)

[3] Uenishi J, Kawahama R, Yonemitsu O, J. Org. Chem., 62, 1691 (1997)

[4] D'Ambra TE, Javitt NB, Nakanishi K, Warchol T, Tetrahedron Lett., 38, 3801 (1997)

[5] Reetz MT, Angew. Chem.-Int. Edit., 23, 556 (1984)

[6] Collum DB, McDonald JH, Still WC, J. Am. Chem. Soc., 102, 2118 (1980)

[7] Nagaoka H, Kishi Y, Tetrahedron, 37, 3873 (1981)

[8] Meyers AI, J. Am. Chem. Soc., 105, 5015 (1983)

[9] Paterson I, Nowak T, Tetrahedron Lett., 37, 8243 (1996)

[10] Cohen N, Eichel WF, Lopresti RJ, Neukom C, Saucy G, J. Org. Chem., 41, 3505 (1976)

[11] Eguchi T, Arakawa K, Terachi T, Kakinuma K, J. Org. Chem., 62, 1924 (1997)

[12] Branca Q, Fischli A, Helv. Chim. Acta, 60, 925 (1977)

[13] Sheldon RA, "Chirotechnology," Marcel Dekker, New York, pp. 362~364 (1993)

[14] Wang YF, Sih CJ, Tetrahedron Lett., 25, 4999 (1984)

[15] Tombo GMR, Schar HP, Fernandez X, Busquets I, Ghisalba O, Tetrahedron Lett., 27, 5707 (1986)

[16] Kitazume T, Sato T, Ishikawa N, Chem. Lett., 1811 (1984)

[17] Bjorkling F, Boutelje J, Gatenbeck S, Hult K, Norin T, Tetrahedron Lett., 26, 4957 (1985)

[18] Luyten M, Muller S, Herzog B, Keese R, Helv. Chim. Acta, 70, 1250 (1987)

[19] Asegawa JH, Ogura M, Hamaguchi S, Shimazaki S, Kawaharada H, Watanabe K, J. Ferment. Technol., 59, 203 (1981)

[20] Goodhue CT, Schaffer JR, Biotechnol. Bioeng., 13, 203 (1971)

[21] Kanegafuchi Chemical Industry Co., Ltd., Jpn. Kokai Tokko Koho JP 3 239 787; Chem. Abstr., 97, 37534f (1982)

[22] Choy W, Ma P, Masamune S, Tetrahedron Lett., 22, 3555 (1981)

[23] Evans DA, Ennis MD, Mathre DJ, J. Am. Chem. Soc., 104, 1737 (1982)

[24] Gennari C, Bernardi A, Scolastico C, Potenza D, Tetrahedron Lett., 26, 4129 (1985)

[25] Roush WR, Adam MA, Peseckis SM, Tetrahedron Lett., 24, 1377 (1983)

[26] Harada T, Hayashiya T, Wada I, Iwa-ake N, Oku A, J. Am. Chem. Soc., 109, 527 (1987)

[27] Ihara M, Takahashi M, Taniguchi N, Fukumoto K, Kametani T, J. Chem. Soc.-Chem. Commun., 619 (1987)

[28] Ihara M, Takahashi M, Taniguchi N, Yasui K, Fukumoto K, J. Chem. Soc.-Perkin Trans. 1, 897 (1989)

[29] Ho TL, "Symmetry: A Basis for Synthesis Design," Wiley, New York (1995)

[30] Miyamoto K, Ohta H, J. Am. Chem. Soc., 112, 4077 (1990)

[31] Miyamoto K, Tsuchiya S, Ohta H, J. Am. Chem. Soc., 114, 6256 (1992)

[32] Kenyon J, Ross WA, J. Chem. Soc., 2307 (1952)

[33] Verbit L, Halbert TF, Patterson RB, J. Org. Chem., 40, 1649 (1975)

[34] Toussaint O, Capdevielle P, Maumy M, Tetrahedron Lett., 28, 539 (1987)

[35] Choi WB, Churchill HRO, Lynch JE, Volante RP, Reider PJ, Shinkai I, J. Org. Chem., 60, 8367 (1995)

[36] Tsuji J, Nisar M, Minami I, Tetrahedron Lett., 27, 2483 (1986)

[37] Avramoff M, Sprinzak Y, J. Org. Chem., 26, 1284 (1961)

[38] Bohme H, Teltz TP, Arch. Pharm., 288, 343 (1955)

[39] Carey FA, Giuliano RM, J. Org. Chem., 46, 1366 (1981)

[40] Breslow DS, Baumgarten E, Hauser CR, J. Am. Chem. Soc., 66, 1286 (1944)

[41] Gutman AL, Boltanski A, Tetrahedron Lett., 26, 1573 (1985)

[42] Darensbourg DJ, Holtcamp MW, Khandelwal B, Klausmeyer KK, Reibenspies JH, Inorg. Chem., 34(9), 2389 (1995)

[43] Reference 5, p. 166