【药物名称】Ceftizoxime alapivoxil, AS-924, KY-020
化学结构式(Chemical Structure):
参考文献No.14915
标题:Cephalosporin cpds. and production thereof
作者:Muro, H.; Kasai, M.; Hatano, s.; Nishimura, K.-I.; Nishizawa, S.; Kakeya, N. (Kyoto Pharmaceutical Industries, Ltd.)
来源:EP 0497978; JP 1991204883; US 5389625; WO 9106549
合成路线图解说明:

Coupling of ethyl glyoxylate derivative (I) with Boc-L-Alanine (II) by means of EDC and DMAP in DMF provides compound (III), whose ethyl ester is subjected to saponification by treatment with NaOH in EtOH to furnish carboxylic acid (IV). Condensation of (IV) with methoxyamine (NH2OMe) in THF/H2O yields methoxyimino acetic acid derivative (V), which is then coupled to pivaloyloxymethyl 7-amino-3-cephem-4-carboxylate (VI) in CH2Cl2 by means of phosphorus oxychloride (POCl3) in DMF/EtOAc and N-trimethylsilylacetamide to give compound (VII). Finally, the desired compound is obtained after treatment of (VII) with TFA and anisole in CH2Cl2 for Boc removal . Alternatively, methoxyimino acetic acid derivative (V) can be converted into intermediate (VII) by coupling with 7-amino-3-cephem-4-carboxylic acid (VIII) by means of POCl3 in DMF/EtOAc and N-trimethylsilylacetamide in CH2Cl2 to provide derivative (IX), followed by condensation with iodomethyl pivalate (X) by means of potassium acetate in DMF.

合成路线图解说明:

Coupling of pivaloyloxymethyl 7-amino-3-cephem-4-carboxylate (VI) and methoxyimino acetic acid derivative (XI) by means of POCl3 and pyridine in CH2Cl2 gives compound (XII) (alternatively (XII) can be obtained by condensation of ceftizoxime (CZX) (XIII) with iodomethyl pivalate (X) in N,N-dimethylacetamide (DMAc) in the presence of dicyclohexylamine). Coupling of (XII) with Boc-L-alanine (II) by means of EDC and DMAP in CH2Cl2 gives intermediate (VII), whose Boc protecting group is removed by treatment with either HCl/isopropanol in formic acid or TFA and anisole in CH2Cl2. Yet another strategy can be followed, involving the coupling of pivaloyloxymethyl 7-amino-3-cephem-4-carboxylate (VI) with derivative (XIV) by means of Et3N in N,N-dimethylacetamide.

参考文献No.536841
标题:AS-924, a novel bifunctional prodrug of ceftizoxime
作者:Kasai, M.; Hatano, S.; Kitagawa, M.; Yoshimi, A.; Shirahase, H.; Nishimura, K.; Kakeya, N.
来源:J Antibiot 1999,52(5),491
合成路线图解说明:

Coupling of pivaloyloxymethyl 7-amino-3-cephem-4-carboxylate (VI) and methoxyimino acetic acid derivative (XI) by means of POCl3 and pyridine in CH2Cl2 gives compound (XII) (alternatively (XII) can be obtained by condensation of ceftizoxime (CZX) (XIII) with iodomethyl pivalate (X) in N,N-dimethylacetamide (DMAc) in the presence of dicyclohexylamine). Coupling of (XII) with Boc-L-alanine (II) by means of EDC and DMAP in CH2Cl2 gives intermediate (VII), whose Boc protecting group is removed by treatment with either HCl/isopropanol in formic acid or TFA and anisole in CH2Cl2. Yet another strategy can be followed, involving the coupling of pivaloyloxymethyl 7-amino-3-cephem-4-carboxylate (VI) with derivative (XIV) by means of Et3N in N,N-dimethylacetamide.

参考文献No.546568
标题:AS-924, a novel orally active bifunctional prodrug of ceftizoxime. Synthesis and relationship between physicochemical properties and oral absorption
作者:Kasai, M.; Hatano, S.; Kitagawa, M.; Yoshimi, A.; Nishimura, K.; Mori, N.; Sakai, A.; Sugihara, T.
来源:Chem Pharm Bull 1999,47(8),1081
合成路线图解说明:

Coupling of pivaloyloxymethyl 7-amino-3-cephem-4-carboxylate (VI) and methoxyimino acetic acid derivative (XI) by means of POCl3 and pyridine in CH2Cl2 gives compound (XII) (alternatively (XII) can be obtained by condensation of ceftizoxime (CZX) (XIII) with iodomethyl pivalate (X) in N,N-dimethylacetamide (DMAc) in the presence of dicyclohexylamine). Coupling of (XII) with Boc-L-alanine (II) by means of EDC and DMAP in CH2Cl2 gives intermediate (VII), whose Boc protecting group is removed by treatment with either HCl/isopropanol in formic acid or TFA and anisole in CH2Cl2. Yet another strategy can be followed, involving the coupling of pivaloyloxymethyl 7-amino-3-cephem-4-carboxylate (VI) with derivative (XIV) by means of Et3N in N,N-dimethylacetamide.

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