The X-ray and NMR studies on the regio- and stereoselective courses for insertion of ketones into the s-cis- and s-trans-diene complexes of zirconium leading to (Z)-1,2-oxazirconacyclohept-4-enes.

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• The <I>s</I>-<I>trans</I>-diene coordination in (η<SUP>5</SUP>-C<SUB>5</SUB>Me<SUB>5</SUB>)<SUB>2</SUB>Zr(butadiene) and the <I>s</I>-<I>cis</I>-diene coordination in (η<SUP>5</SUP>-C<SUB>5</SUB>Me<SUB>5</SUB>)<SUB>2</SUB>Zr(isoprene) were confirmed by the <SUP>1</SUP>H- and <SUP>13</SUP>C-NMR spectral studies. The reaction of 2,4-dimethyl-3-pentanone with these complexes occurred regio- and stereoselectively to give (<U>Remark: Graphics omitted.</U>) (<B>5</B>: R=H, <B>6</B>: R=Me). The X-ray crystal structure analysis of <B>5</B> and <B>6</B> revealed the (<I>Z</I>)-configuration with respect to the olefin part. Crystal data for <B>5</B>: monoclinic, space group <I>P</I>2<SUB>1</SUB>/<I>n</I> with <I>Z</I>=4, <I>a</I>=11.650(2), <I>b</I>=17.791(3), <I>c</I>=13.612(2) Å, β=92.20(2)°, <I>R</I>=0.111 for 4308 non-zero reflections. Crystal data for <B>6</B>: monoclinic, space group <I>P</I>2<SUB>1</SUB>/<I>n</I> with <I>Z</I>=4, <I>a</I>=10.279(3), <I>b</I>=30.177(4), <I>c</I>=9.955(2) Å, β=108.67(2), <I>R</I>=0.104 for 3526 non-zero reflections.

• 公益社団法人 日本化学会の論文

著者

• Miki Kunio

  Department Of Chemistry Graduate School Of Science Kyoto University

• Kai Yasushi

  Department Of Applied Chemistry Faculty Of Engineering Osaka University

• Yasuda Hajime

  Department Of Applied Chemistry Faculty Of Engineering Hiroshima University

• Kanehisa Nobuko

  Department Of Applied Chemistry Faculty Of Engineering Osaka University

• Kasai Nobutami

  Department Of Applied Biological Science Tokyo University Of Science

• Nakamura Akira

  Department Oc Macromolecular Science Faculty Of Science Osaka University

• Akita Munetaka

  Department of Macromolecular Science, Faculty of Science, Osaka University

• Miki Kunio

  Department of Applied Chemistry, Faculty of Engineering, Osaka University

• Yasuda Hajime

  Department of Macromolecular Science, Faculty of Science, Osaka University

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