A simple asymmetric synthesis of (+)- and (−)-2,6-diaminopimelic acids

Author:

Paradisi Francesca,Porzi Gianni,Rinaldi Samuele,Sandri* Sergio

Publisher

Elsevier BV

Subject

Inorganic Chemistry,Organic Chemistry,Physical and Theoretical Chemistry,Catalysis

Reference10 articles.

1. Williams, R. M.; Fegley, G. J.; Gallegos, R.; Schaefer, F.; Pruess, D. L. Tetrahedron 1996, 52, 1149 and references cited therein.

2. Gelb, M. H.; Lçin, Y.; Pickard, M. A.; Song, Y.; Vederas, J. C. J. Am. Chem. Soc. 1990, 112, 4932; Williams, R. M.; Im, M.-N.; Cao, J. J. Am. Chem. Soc. 1991, 113, 6976; Williams, R. M.; Yuan, C. J. Org. Chem. 1992, 57, 6519; Abbott, S. D.; Lane-Bell, P.; Sidhu, K. P. S.; Vederas, J. C. J. Am. Chem. Soc. 1994, 116, 6513; Song, Y.; Niederer, D.; Lane-Bell, P. M.; Lan, L. K. P.; Crawley, S.; Palcic, M. M.; Pickard, M. A.; Pruess, D. L.; Vederas, J. C. J. Org. Chem. 1994, 59, 5784; Bull, S. D.; Chernega, A. N.; Davies, S. G.; Moss, W. O.; Parkin, R. M. Tetrahedron 1998, 54, 10379 and references cited therein.

3. Porzi, G.; Sandri, S. Tetrahedron: Asymmetry 1996, 7, 189; Favero, V.; Porzi, G.; Sandri, S. Tetrahedron: Asymmetry 1997, 8, 599; Porzi, G.; Sandri, S. Tetrahedron: Asymmetry 1998, 9, 3411; Carloni, A.; Porzi, G.; Sandri, S. Tetrahedron: Asymmetry 1998, 9, 2987; Di Felice, P.; Maestri, M.; Paradisi, F.; Porzi, G.; Sandri, S. Tetrahedron: Asymmetry 1999, 10, 4709.

4. Porzi, G.; Sandri, S. Tetrahedron: Asymmetry 1994, 5, 453.

5. After chromatography of the crude reaction (eluting with hexane/ethyl acetate) in addition to the 1,3-diiodopropane the byproduct 7 was isolated in about 10% yield, while the separation of diastereomers of 2 was unsuccessful. However, the subsequent cyclization reaction6 leads to easily separable diastereomers 3 and 4. The structure of 7 was determined by 1H NMR spectroscopic data and further corroborated by smooth conversion into 6 with refluxing 57% HI. (1′S,2S)-1,3-Bis-[1,4-N,N-(1′-phenethyl)-3,6-diketopiperazin-2-yl]-propane 7: 1H NMR δ (CDCl3) 1.5 (d, 6H, J=7.2 Hz), 1.6 (d, 6H, J=7.2 Hz), 1.6 (m, 2H), 1.85 (m, 4H), 3.56 (d, 2H, J=17.4 Hz), 3.68 (dd, 2H, J=4.5, 8.4 Hz), 3.94 (d, 2H, J=17.4 Hz), 5.78 (q, 2H, J=7.2 Hz), 5.8 (q, 2H, J=7.2 Hz), 7.3 (m, 20ArH); 13C NMR δ (CDCl3) 15.2, 17.3, 21, 33.1, 44.4, 49.7, 51.8, 56.8, 126.8, 127.8, 127.9, 128.6, 128.7, 138.5, 138.9, 165, 165.9; [α]D −176.1 (c 1.01, CHCl3).

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