Studies on π-Face Selective Additions with 3,4-Di-tert-butylthiophene 1-Oxide and 1-Imide
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概要
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3, 4-Di-<I>tert</I>-butylthiophene 1-oxide (1) and 1-imide (2), which possess <I>anti</I>- and <I>syn</I>-π-faces with respect to the S=X bond (X= O or NTs), provide an excellent model system to investigate π-face selectivity in a variety of addition reactions. Diels-Alder reactions of 1, including inverse electron-demand and hetero Diels-Alder reactions, all take place selectively at the <I>syn</I>-π-face of 1 with respect to the S=O bond in high yields under mild conditions. The observed π-face selectivity can be well explained by the difference in conformational changes that are brought about at the transition states for <I>anti</I>- and <I>syn</I>-π-face additions. Even 1, 3-dipolar cycloadditions of 1 take place predominantly at the <I>syn</I>-π-face to the S=O bond. Diels-Alder reactions of 2 also occur at the <I>syn</I>-π-face with respect to the S=NTs bond. The Diels-Alder reaction of 2 with PTAD provides the first synthesis of an <I>S</I>-unoxidized 1, 2-thiazetidine derivative. The addition of bromine to 1, though not π-face selective, occurs in a 1, 4-<I>cis</I> mode exclusively. Only Michael additions to 1 take place at the <I>anti</I>-π-face probably as a result controlled by nonequivalent orbital extension of π-LUMO.
- 社団法人 有機合成化学協会の論文
- 2003-11-01
著者
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NAKAYAMA Juzo
Department of Chemistry, Graduate School of Science and Engineering, Saitama University
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Nakayama J
Department Of Chemistry Faculty Of Science Saitama University
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Nakayama J
Department Of Chemistry Graduate School Of Science And Engineering Saitama University
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Nakayama Juzo
Department Of Chemistry School Of Science And Engineering Saitama University
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Nakayama Juzo
Department Of Chemistry Faculty Of Science Saitama University
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