Synthetic Studies of Laurencin and Related Compounds. I. The Synthesis of <I>t</I>-3-Bromo-<I>r</I>-2,<I>c</I>-8-diethyl-3,4,7,8-tetrahydro-2<I>H</I>-oxocin
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概要
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The synthesis of the titled bromohydrooxocin (<B>2</B>), one of model compounds for synthetic approaches to laurencin (<B>1</B>), is described, <I>trans</I>- and <I>cis</I>-2,5-Diethyl-2,5-dihydrofurans (<B>25</B>), prepared by treatment of furan with bromine and then with ethyl magnesium bromide, was submitted, after oxidation with ozone, to the Robinson-Schöpf condensation with methylamine to give <I>trans</I>- and <I>cis</I>-2,4-diethylbicyclononanones (<B>19a</B> and <B>19b</B>), whose configurations were discussed on the NMR spectra. These compounds were converted into <I>trans</I>- and <I>cis</I>-diethylhydrooxocinones (<B>38a</B> and <B>38b</B>), respectively, according to a six-step process analogous to the Paguette procedure. It is to be noted that (i) thermally induced, intramolecular dienyl 1,5-hydrogen transfer (<B>36</B> to <B>37</B>), one of the key reactions in the process, took place without difficulty with <I>cis</I>-aminodiene (<B>36b</B>), while the rearrangement did not proceed smoothly with <I>trans</I>-aminodiene (<B>36a</B>), and (ii) <I>trans</I>-ketone (<B>38a</B>) was isomerized readily into <I>cis</I>-ketone (<B>38b</B>). Further hydride reduction of <I>cis</I>-ketone (<B>38b</B>) followed by bromination with carbon tetrabromide and triphenylphosphine yielded the aimed bromohydrooxocin (<B>2</B>) as a major product, which possessed the same relative configuration concerning the ring substituents as laurencin (<B>1</B>).
- 公益社団法人 日本化学会の論文
著者
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Numata Satoshi
Department Of Environmental Biology And Chemistry Faculty Of Science University Of Toyama
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Masamune Tadashi
Department Of Chemistry Faculty Of Science Hokkaido University
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Sato Takehiro
Department Of Applied Chemistry Faculty Of Technology Tokyo University Of Agriculture And Technology
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Matsue Hajime
Department Of Cardiovascular Medicine Kyoto Prefectural University School Of Medicine
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Matsuyuki Akira
Department of Chemistry, Faculty of Science, Hokkaido University
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Murase Hisashi
Department of Chemistry, Faculty of Science, Hokkaido University
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Numata Satoshi
Department of Chemistry, Faculty of Science, Hokkaido University
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