Abstract
A new three-step synthesis to 3-hydroxy-2-pyrrolidinones starting from β-amino acids has been developed. The key step is a novel reductive photocyclization.
Key words
3-hydroxy-2-pyrrolidinone - 4-hydroxypyroglutamic acid - α-keto ester - β-amino acid - reductive photocyclization
References
1a
Michael JP.
Nat. Prod. Rep.
2004,
21:
625
1b
Michael JP.
Nat. Prod. Rep.
2003,
20:
458
2 Aschwanden W, and Kyburz E. inventors; Hoffmann-La Roche & Co. Europ. Patent 0071216.
; Chem. Abstr. 1983 , 98 , 160582t
3a Zhang J, Huang L, Wu K, and Chen S. inventors; US Pat. Appl. Publ., 207935.
3b Dushin RG, and Trybulski EJ. inventors; PCT Int. Appl., WO 9906351.
3c Cox JM, Gillen KJ, Ellis RM, Vohra SK, Smith SC, and Matthews IR. inventors; PCT Int. Appl., WO 9637466.
4a
Naito T.
Nakagawa S.
Abe Y.
Toda S.
Fujisawa K.
Miyaki T.
Koshiyama H.
Ohkuma H.
Kawaguchi H.
J. Antibiot.
1973,
26:
297
4b
Ringdahl B.
Craig JC.
Acta Chem. Scand. B
1980,
34:
731
4c
Goel OP.
Krolls U.
Lewis EP.
Org. Prep. Proced. Int.
1985,
17:
91
4d
Hua DH.
Miao SW.
Bharathi SN.
Katsuhira T.
Bravo AA.
J. Org. Chem.
1990,
55:
3682
4e
Bentley JM.
Wadsworth HJ.
Willis CL.
J. Chem. Soc., Chem. Commun.
1995,
231
4f
Pires R.
Burger K.
Tetrahedron
1997,
53:
9213
4g
Kamal A.
Venkata Ramana K.
Venkata Ramana A.
Hari Babu A.
Tetrahedron: Asymmetry
2003,
14:
2587
4h
Huang P.-Q.
Zheng X.
Wei H.
Heterocycles
2003,
60:
1833
5
Wasserman HH.
Ho W.-B.
J. Org. Chem.
1994,
59:
4364
6
General Irradiation Procedure.
The α-keto ester modified β-amino acids (2 or 4 ) were dissolved in 200 mL CH2 Cl2 in a 250 mL pyrex flask. The solution was degassed with argon during 30 min and irradiated with a cooled 180 W mercury high-pressure lamp, which was immersed in the solution. After the photoreaction was finished the solvent was evaporated, and the residue purified by column chromatography yielding the pure 3-hydroxy-2-pyrrolidinones (3 ) or the 4-hydroxypyroglutamic acids (6 ). Spectroscopic data for 3a as an example: 1 H NMR (400 MHz, CDCl3 ): δ = 1.53 (s, 9 H), 1.96 (dtd, J = 12.4, 10.5, 9.1 Hz, 1 H), 2.44 (dddd, J = 12.4, 8.2, 6.6, 1.5 Hz, 1 H), 3.31 (br s, 1 H), 3.52 (ddd, J = 10.9, 10.5, 6.6 Hz, 1 H), 3.83 (ddd, J = 10.9, 9.1, 1.5 Hz, 1 H), 4.37 (dd, J = 10.5, 8.2 Hz, 1 H). 13 C NMR (101 MHz, CDCl3 ): δ = 27.1 (CH2 ), 28.1 (CH3 ), 42.2 (CH2 ), 70.7 (CH), 83.6 (C), 149.9 (C), 174.8 (C). MS (ESI): m/z (%) = 425 (29) [2 M + Na]+ , 224 (100) [M + Na]+ , 168 (48) [M - t -Bu + Na]+ .
7a
Merino P.
Revuelta J.
Tejero T.
Chiacchio U.
Rescifina A.
Piperno A.
Romeo G.
Tetrahedron: Asymmetry
2002,
13:
167
7b
Heinz LJ.
Lunn WHW.
Murff RE.
Paschal JW.
Spangle LA.
J. Org. Chem.
1996,
61:
4838
8
Zhang X.
Schmitt AC.
Jiang W.
Tetrahedron Lett.
2001,
42:
5335
9 Mitchell G, and Vohra SK. inventors; PCT Int. Appl.; WO 9719920.