Synthesis of aminoaldonic acids

Christel Thea Jørgensen

    Research output: Book/ReportPh.D. thesisResearch

    Abstract

    With the aim of synthesising aminoaldonic acids, two 2-acetamido-2-deoxyaldonolactones with D-galacto (6) and D-arabino (11) configuration were prepared from acetylated sugar formazans in analogy with a known procedure. Empolying the same procedure to acetylated sugar phenylhydrazones gave mixtures of 2,5-anhydrides and not the expected 2-acetamido-2-deoxy aldose phenylhydrazones. The acetylated phenylhydrazones were found to eliminate acetic acid when heated in aqueous ethanol and 1-phenylazoalkenes could be isolated by crystallisation. By this method the 17, 20, 23 and 25 were prepared from the phenylhydrazones of D-galactose, D-mannose, L-rhamnose and D-arabinose, respectively. The phenylazoalkenes were selectively reduced with sodium borohydride to give 2-deoxy aldose phenylhydrazones, which were hydrolysed to the corresponding 2-deoxy aldoses. Thus, 2-deoxy-D-lyxo-hexose (33), 2-deoxy-D-arabino-hexose (35), 2,6-dideoxy-L-arabino-hexose (37) and 2-deoxy-D-erythro-hexose (39) were prepared by this new method.Three new 2,3-aziridino-2,3-dideoxyhexonamides 43, 51 and 64 were prepared by a three step procedure from the readily available D-glucono-1,5-lactone, D-gulono-1,4-lactone and L-rhamnono-1,4-lactone, respectively. A 2,3-aziridino-2,3-dideoxypentonamide 70 was also prepared from D-glucono-1,5-lactone. The lactones were converted into methyl 3,4-O-isopropylidene-2-O-sulfonyl esters 42, 50, 62 and 68, which upon treatment with concentrated aqueous ammonia yielded the aziridino compounds. The aziridino amides 43 and 51 were reductively cleaved with hydrazine to give 3-amino-2,3-dideoxyhexonhydrazides 83 and 85, which were easily converted into the corresponding lactone 84 and acid 86. The aziridine ring of 43 and 51 was also opened with acetic acid to give the 3-amino-3-deoxyhexonic acids 79 and 82, respectively. The aminolactone 84 was converted into the corresponding amino sugar 89.With the aim of synthesising substrates for the Pictet-Spengler reaction three 4-aldehydo acetamidodideoxytetronolactones 92, 97 and 103 were prepared by periodate cleavage of the corresponding hexonolactones. These compounds did not react with 2-(3,4-dimethoxyphenyl)ethyl amine 105. Instead the commercially available unsubstituted 4-carboxyl tetronolactone 108 was converted into the 2-(3,4-dimethoxyphenyl)ethyl amides 110 and 111 in two steps. These amides were cyclised by the Bischler-Napieralski cyclisation to give the dihydroisoquinoline lactones 113 and 114, which were reduced to give the target tetrahydroisoquinoline lactones 115, 117 and 118.
    Original languageEnglish
    Place of PublicationKgs. Lyngby, Denmark
    PublisherTechnical University of Denmark
    Number of pages127
    Publication statusPublished - Oct 1997

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