Asymmetric catalytic hydrogenation process for preparation...

Details Asymmetric catalytic hydrogenation process for preparation... Asymmetric catalytic hydrogenation process for preparation...

2003-09-11

2004-12-28

Solola, Taofiq (Department: 1626)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

C549S342000, C549S425000, C560S156000

Reexamination Certificate

active

06835841

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates generally to processes for the synthesis of chiral cyclic &bgr;-aminoesters, such compounds being useful as intermediates for matrix metalloproteinases (MMP) and TNF-&agr; converting enzyme (TACE) inhibitors.
BACKGROUND OF THE INVENTION
The present invention relates to processes for the preparation of chiral cyclic &bgr;-aminoesters, which are useful as intermediates in the preparation of MMP and TACE inhibitors. In particular, the present invention provides a process for the preparation of 4-amino-tetrahydro-4H-pyran-3-carboxylate. The general processes disclosed in the art (e.g., C. Cimarelli et al.
Tetrahedron
-
Asymmetry
1994, 5, 1455) provide 4-amino-tetrahydro-4H-pyran-3-carboxylate in low and inconsistent yields of the desired stereoisomer. In contrast to the previously known processes, the present invention provides more practical and economical methodology for the preparation of (3R,4R)-4-aminotetrahydro-4H-pyran-3-carboxylate in relatively high yield and isomeric purity.
The present invention provides access to such &bgr;-aminoesters with increased selectivity in the reduction step, resulting in higher yields and isomeric purity of products. In contrast to protocols known in the art using borohydrides as reducing agents (D. Xu et al.
Tetrahedron
-
Asymmetry
1997, 8, 1445), throughput has been increased significantly due to low process volumes. Chiral cyclic &bgr;-aminoester products can now be isolated by salt formation directly from the filtered reaction mass, thereby obviating the need for aqueous work-up procedures.
SUMMARY OF THE INVENTION
Accordingly, the present invention provides novel processes for making chiral cyclic &bgr;-aminoesters.
The present invention provides novel hydrobromide salts of the chiral cyclic &bgr;-aminoesters.
These and other objects, which will become apparent during the following detailed description, have been achieved by the inventors' discovery that compounds of formula II can be formed from compounds of formula I (* denotes a chiral center).


REFERENCES:
patent: 062 840 (1982-03-01), None
patent: 250 179 (1987-06-01), None
patent: WO 00/43383 (2000-07-01), None
patent: WO 01/07433 (2001-02-01), None
patent: WO 01/70673 (2001-09-01), None
patent: WO 02/02525 (2002-01-01), None
patent: WO 02/24684 (2002-03-01), None
Cimarelli, C.; Palmieri, G.; Bartoli, G.; “Diastereo and Enantioselective Entry to &bgr;-Amino Esters by Hydride Reduction of Homochiral &bgr;-Enamino Esters”, Tetrahedron: Asymmetry, vol. 5, No. 8, pp. 1455-1458, 1994.
Xu, D.; Prasad, K.; Repi{hacek over (c)}, O.; Blacklock, T. J.; “A practical synthesis of anantiopure ethyl cis-2-amino-1-cyclohexanecarboxylate via asymmetric reductive amination methodology”, Tetrahedron: Asymmetry, vol. 8, No.9, pp. 1445-1451, 1997.
Melillo, D. G.; Shinkai, I.; Liu, T., “A practical synthesis of (±)-Thienamycin”, Tetrahedron Lett., vol. 21, 1980, pp. 2783-2786.
Melillo, D. G.; Cvetovich, R. J.;Ryan, K. M.; Sletzinger, M., “An Enantioselective Approach to (+)-Thienamycin from Dimethyl 1,3-Acetonedicarboxylate and (+)-&agr;-Methylbenzylamine”, J. Org. Chem. 1986, 51, pp. 1498-1504.
Haviari, G.; Céléier, J. P.; Lhommet, G.; Gardette, D.; Gramain, J. C.;“ Asymmetric Synthesis with Chiral Hydrogenolysable Amines. Cyclic &bgr;-Enamino Ester Reduction A Diastereoselective Route to 2,3-Disubstituted Pyrrolidines”, Tetrahedron Lett., vol. 33, pp. 4311-4312, 1992.
Haviari, G; Célérier, J. P.; Petit, H.; Lhommet, G.; “Asymmetric Synthesis with Chiral Hydrogenolysable Amines. A Short Synthesis of (−) Isoretronecanol”, Tetrahedron Lett., vol. 34., No. 10, pp. 1599-1600, 1993.
Agami, C.; Kadouri-Puchot, C.; Le Guen, V.; Vaissermann, J., “Neuromediator Analogs: Synthesis of cis (2R,3S) and trans (2S,3S)-2,3-Piperidine Dicarboxylic Acids from (2S)-2-Phenylglycinol”, Tetrahedron Lett., vol. 36, No. 10, pp. 1657-1660, 1995.
Cimarelli, C.; Palmieri, G.; “Stereoselective Reduction of Anantipure &bgr;-Anamino Esters by Hydride: A Convenient Synthesis of Both Enantiopure &bgr;-Amino Esters”, J. Org. Chem. 1996, 61, pp. 5557-5563.
Hayashi, Y.; Rhode, J.J.; Corey, E.J.; “A Novel Chiral Super-Lewis Acidic Catalyst for Anantioselective Synthesis”, J. Am. Chem. Soc. 1996, 118, pp. 5502-5503.
Agami, C.; Hamon, L.; Kadouri-Puchot, C.; Le Guen, V.; “Enantioselective Synthesis of Conformationally Restricted Analogs of NMDA: cis- and trans-Piperidine-2,3-dicarboxylic Acids and Methylated Derivatives”, J. Org. Chem. 1996, 61, pp. 5736-5742.
Segat, F.; Lingibé, O.; Graffe, B.; Sacquet, M.C.; Lhommet, G.; “Asymmetric Synthesis with Chiral Hydrogenolysable Amines: A New Route to Enantiomerically Pure Amino Diols”, Heterocycles, vol. 45, No. 8, pp. 1451-1455, 1997.
Blot, J.; Bardou, A.; Bellec, C.; Fargeau-Bellassoued, M. C.; Célérier, J. P.; Lhommet, G.; Gardette, D.; Gramain, J. C.; “Chiral Cyclic &bgr;-AMino Esters. Part II: Synthesis by Diastereoselective Reduction of Anamino Esters”, Tetrahedron Lett. , vol. 38, No. 49, pp. 8511-8514, 1997.
Daley, V.; d'Angelo, J.; Cave, C.; Mahuteau.J.; Chiaroni, ,A.; Riche, C.; “A Novel Asymmetric Synthesis of 2,5-Dialkylpyrrolidines”, Tetrahedron Letter, vol. 40, pp. 1657-1660, 1999.
David, O et al., “Enamino Ester Reduction: A Short Enantioselective Route to Pyrrolizidine and Indolizidine Alkaloids. Synthesis of (+)-Laburnine, (+)-Tashiromine, and (−)-Isoretronecanol”, J. Org. Chem. 1999, 64, 3122-3131.
Zhong, H. M.; Cohen, J. H.; Abdel-Magid, A. F.; Kenney, B. D.; Maryanoff, C. A.; Shah, R. D.; Villani, F. J., Jr.; Zhang, F.; Zhang, X.; “An efficient stereoselective synthesis of methyl (S)-3-amino-3-(3-pyridyl)propanoate”, Tetrahedron Lett. 1999,40, 7721-7725.
Mechelke, M. F.; Meyers, A. I.; “An efficient, asymmetric synthesis of (+)-euphoccoccine”, Tetrahedron Lett. 2000,41, 4339-4342.
David, O.; Bellec, C.; Fargeau-Bellassoued; Lhommet, G.; “Diastereoselective reduction of chiral enaminolactones: A short and convenient route to anantiopure(+)-tashiromine”, Heterocycles, vol. 55, No. 9, 1689-1701, 2001.
Wang, G. T., et al; “Design, Synthesis, and Structural Analysis of Influenza Neuraminidase Inhibitors Containing Pyrrolidine Cores”, J. Med. Chem. 2001, 44, 1192-1201.

Affiliated with

Also associated with

Rating

Asymmetric catalytic hydrogenation process for preparation... does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Asymmetric catalytic hydrogenation process for preparation..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Asymmetric catalytic hydrogenation process for preparation... will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-3295062