Optically active 3-(1-(alkylamino))alkyl pyrrolidines

Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...

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540362, C07D20508

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active

057736103

DESCRIPTION:

BRIEF SUMMARY
FIELD OF THE INVENTION

This method allows the convenient, large scale preparation for compounds, possibly used as intermediates of quinolones, in high optical purity and good yield. Previously published methods lack adequate stereoselectivity for large scale preparation or are impractical for large scale preparation.


BACKGROUND OF THE INVENTION

The quinolonecarboxylic acid based antibacterial agents such as norfloxacin and ciprofloxacin, now used clinically, exhibit potent antibacterial activity. Efforts to synthesize or discover a quinolone based antibacterial compound exhibiting maximum antibacterial properties and minimum toxic side effects continue. Many investigators have focused their efforts on developing quinolones with aminoalkyl pyrrolidinyl moieties attached to the 7 position of the quinolone.
Within the chiral environment of living organisms, individual stereoisomers of biologically active compounds are often known to have unique properties relative to their related stereoisomers. In vitro and in vivo studies of quinolone derivatives with various aminoalkyl pyrrolidinyl 7 position side chains have shown that the activity of these compounds can be strongly influenced by the stereochemical positions of the atoms in the side chain. European Patent Application - Publication 0,443,498 A1, published 28 Aug. 1991, discloses an aminoalkyl pyrrolidinyl 7 position side chain quinolones having 2 asymmetric carbon atoms on a 3-amino-4-methylpyrrolidine ring attached to the 7 position of a quinolone. Two of the four possible stereochemical isomers were two to six times more active than the other two stereoisomers. U.S. Pat. No. 5,157,128, issued 20 Oct. 1992, (Hagen) describes the effect of stereospecific alkylation at the 1'-aminoethyl position of a 3-pyrrolidine substituent also substituted at the 7 position of a quinolone. Hagen reported that the R-(1,1-dialkylated-1-aminomethyl)pyrrolidine, when coupled at the 7 position of a quinolone leads to antibacterial agents with improved activity and safety.
This invention relates to a process for the synthesis of various optically active amino pyrrolidinyl stereoisomers, or enantiomers, that may be attached to quinolonecarboxylic acids or naphthyridones. The process disclosed by the procedures and examples herein allow the synthesis of these side chains in a more efficient manner than any previously disclosed method of synthesis. Novel intermediates are also disclosed.


INFORMATION DISCLOSURE

Kokai Patent Application No. Hei 3 (1991)-72476, discloses the preparation of similar compounds using a less selective method of synthesis. Another less selective method of synthesis is provided in the Journal of Heterocyclic Chemistry, Vol. 29, No. 6, pp. 1481-98 (1992), also mentioned below. U.S. Pat. No. 5,157,128 issued 20 Oct., 1992, (Hagen), discloses optically pure isomers of 7-(3-(1,1-dialkylmethyl-1-amino)-1-pyrrolidinyl quinolones and naphthyridones and their method of manufacture. Guanti, Giuseppe, et al. in Tetrahedron Letter, Vol. 28, No. 37, pp. 4335-4338 (1987) discuss a stereocontrolled synthesis of 3-(1'-hydroxyethyl)-2-azetidinones through trimethylsilyl trifluoromethanesulphonate catalyzed condensation of silyl ketene acetal. Estermann and Seebach, Helvetica Chimica Acta, Vol. 71 pp. 1824-39 (1988) discloses diastereoselective alkylation of N-protected 3-aminobutanoic acid esters at the 2 position. Seebach and Esterman, Tetrahedron Letters, Vol.28, No. 27 pp. 3310-3106 (1987) add additional discussion concerning alkylation of benzaldehyde to give enantiomerically pure 3-aminobutanoic acid derivatives. Furukawa et. al., Chemical Pharmaceutical Bulletin, Vol. 27. pp. 2223-6 at 6 (1979) discloses the use of Pearlman's reagent, 10% palladium hydroxide on charcoal, to hydrogenolytically remove benzyl groups from amines. The protection of the amino group with protecting groups such as carboxy benzyl are disclosed in Helvetica Chimica Acta, Vol. 66, Fasc. 2, Nr. 38, p. 461 (1983). Davies, in both Tetrahedron:Asymmetry, Vol. 2, No. 3, pp. 183-186 (1991) an

REFERENCES:
patent: 5157128 (1992-10-01), Hagen et al.
Guanti, Giuseppe, et al, in Tetrahedron Letters 28 (37), pp. 4335-4338 (1987).
Seebach and Esterman, Tetrahedron Letters, 28, 27, pp. 3103-3106 (1987).
Database WPI Week 9119, Derwent Publication Ltd. aN 91-136059 and JP A 3 072 476, 1991.
Hagen, Susan E., et al., Journ. of Medicinal Chem., 37, 6, pp. 733-738 (1994).
Domagala, John M., et al., Journ. of Medicinal Chem., 36, 7, pp. 871-882 (1993).
Plummer, Janet S., et al., Tetrahedron Letters, 34, 47, pp. 7529-7532 (1993).
Archelas, A., et al., Tetrahedron Letters, 29, 50, pp. 6611-6614 (1988).
Liebeskind, Lanny S., et al., Journ of the American Chem. Soc., 108, 29, pp. 6328-6343 (1986).
M. C. Schroeder, et al., Journal of Heterocyclic Chemistry, vol. 29, No. 6, pp. 1481-1498 (1992).
V. Estermann, et al., Helvetica Chimica Acta, vol. 71, pp. 1824-1839 (1988).
M. Furukawa et al., Chemical Pharmaceutical Bulletin, vol. 27(9), pp. 2223-2226 at 6 (1979).
Helvetica Chimica Acta, vol. 66, Fasc. 2, Nr. 38, p. 461 (1983).
S. Davies, et al., Tetrahedron: Asymmetry, vol. 2, No. 3, pp. 183-186 (1991).
S. Davies, "Chiral Lithium Organoamide Technology Available," from Oxford Asymmetry Limited, Oxfordshire, UK., 1991.
F. Orsini, et al., Synthetic Communications, vol. 12, No. 14, pp. 1147-1154 (1982).
F. A. Davis, etal., Journal of the American Chemical Society, vol. 109, No. 11, pp. 3370-3377 (1987).

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