Intramolecular Cyclization of Ene‐Imine Using Dibutylzirconocene.
Intramolecular Cyclization of Ene‐Imine Using Dibutylzirconocene.
复制标题
使用二丁基二茂锆进行烯亚胺的分子内环化。
DOI：
10.1002/chin.200504077
复制
发表时间：
2005
期刊：
影响因子：
--
通讯作者：
M. Mori*
中科院分区：
文献类型：
--
作者：
Muneyoshi Makabe;Y. Sato;M. Mori*
研究了烯亚胺与Cp_2ZrBu_2的反应。以烯醛和伯胺为原料，在MgSO 4存在下合成的亚胺粗品，与Cp2 ZrBu2在室温下反应过夜，沿着少量顺式取代环戊烷衍生物，以高产率得到了反式取代环戊烷衍生物。顺式锆酸盐可能是热力学产物。使用各种烯亚胺进行反应。由烯醛和tBuNH_2合成烯亚胺时，只生成具有顺式取代基的环戊烷。在该反应中，使用手性胺，并进行烯亚胺的非对映选择性环化。结果，在环化化合物氢解后，以光学活性形式获得具有顺式取代基的环戊烷衍生物。
The reaction of ene-imine with Cp2ZrBu2was carried out. When a crude imine, which was prepared from ene-aldehyde and primary amine in the presence of MgSO4, was treated with Cp2ZrBu2at room temperature overnight, cyclopentane derivative havingtrans-substituents was obtained in high yield along with a small amount of cyclopentane derivative havingcis-substituents. Presumably,cis-zirconacycle is a thermodynamic product. Reactions using various ene-imines were carried out. In the case of ene-imine prepared from ene-aldehyde andtBuNH2, only cyclopentane havingcis-substituents was produced. In this reaction, chiral amine was used, and diastereoselective cyclization of ene-imine was carried out. As a result, cyclopentane derivative havingcis-substituents was obtained in an optically active form after hydrogenolysis of the cyclized compound.