Stereospecific Synthesis of C2 Symmetric Diamines from the Mother Diamine by Resonance-Assisted Hydrogen-Bond Directed Diaza-Cope Rearrangement

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• 作者：Hyunwoo Kim ; Yen Nguyen ; Cindy Pai-Hui Yen ; Leonid Chagal ; Alan J. Lough ; B. Moon Kim ; Jik Chin
• 刊名：Journal of the American Chemical Society
• 出版年：2008
• 出版时间：September 10, 2008
• 年：2008
• 卷：130
• 期：36
• 页码：12184-12191
• 全文大小：400K
• 年卷期：v.130,no.36(September 10, 2008)
• ISSN：1520-5126

文摘

Sixteen diphenylethylenediamine analogues including those with electron donating, electron withdrawing, and sterically bulky substituents have been prepared in good overall yields (70∼90%) and in enantiomerically pure form (>99% ee) by diaza-Cope rearrangement reaction. A single chiral mother diamine, ((R,R)-1,2-bis-(2-hydroxyphenyl)-1,2-diaminoethane), is reacted with appropriate aldehydes to form the initial diimines that rearrange to give all the product diimines in the (S,S) form. The daughter diamines are obtained by hydrolysis of the product diimines. Density functional theory computation shows that resonance-assisted hydrogen-bond is the main driving force behind all the rearrangement reactions. Chiral high performance liquid chromatography and circular dichroism spectroscopy show that the highly stereospecific rearrangement reactions take place with apparent inversion of stereochemistry.