Stereospecific synthesis of C2 symmetric diamines from the mother diamine by resonance-assisted hydrogen-bond directed diaza-Cope rearrangement
Stereospecific synthesis of C2 symmetric diamines from the mother diamine by resonance-assisted hydrogen-bond directed diaza-Cope rearrangement
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DOI：
10.1021/ja803951u
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发表时间：
2008-09-10
影响因子：
15
通讯作者：
Chin, Jik
中科院分区：
文献类型：
--
作者：
Kim, Hyunwoo;Nguyen, Yen;Chin, Jik
通过二氮杂-Cope 重排反应，已制备了 16 种二苯基乙二胺类似物，包括具有给电子、吸电子和空间大取代基的化合物，总收率良好（70 至 90%），且呈对映体纯形式（> 99% ee）。单一手性母二胺（(RR)-1,2-双-(2-羟基苯基)-1,2-二氨基乙烷）与适当的醛反应形成初始二亚胺，该初始二亚胺重新排列得到（S,S）形式的所有产物二亚胺。子二胺通过产物二亚胺的水解获得。密度泛函理论计算表明，共振辅助氢键是所有重排反应背后的主要驱动力。手性高效液相色谱和圆二色光谱表明，发生了高度立体特异性的重排反应，并具有明显的立体化学反转。
Sixteen diphenylethylenediamine analogues including those with electron donating, electron withdrawing, and sterically bulky substituents have been prepared in good overall yields (70 similar to 90%) and in enantiomerically pure form (>99% ee) by diaza-Cope rearrangement reaction. A single chiral mother diamine, ((RR)-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.