源自反式-1,2-二氨基环己烷的手性大环脂肪族低聚亚胺。

Chiral macrocyclic aliphatic oligoimines derived from trans-1,2-diaminocyclohexane.

作者信息

Kwit Marcin, Plutecka Agnieszka, Rychlewska Urszula, Gawroński Jacek, Khlebnikov Alexander F, Kozhushkov Sergei I, Rauch Karsten, de Meijere Armin

机构信息

Department of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, 60-780 Poznan, Poland.

出版信息

Chemistry. 2007;13(31):8688-95. doi: 10.1002/chem.200700648.

DOI:10.1002/chem.200700648

PMID:17661323

Abstract

Aliphatic dialdehydes of rigid structures having a cyclohexane, a bicyclo[2.2.2]octane or a [7]triangulane skeleton, have been condensed with enantiomerically pure trans-1,2-diaminocyclohexane to give [3+3] or [2+2] macrocyclization products. Unlike acyclic aliphatic imines, these macrocyclic oligoimines show enhanced stabilities and their structures in the crystals could be determined by X-ray diffraction analyses. The enantiomerically pure [7]triangulane dialdehyde showed remarkable diastereoselectivity in the condensation with the two enantiomers of trans-1,2-diaminocyclohexane: only one of the enantiomers gave a [2+2] macrocyclization product. Circular dichroism measurements combined with computational analysis show that the lowest energy electronic transition in these cyclic oligoimines is of n-pi* type.

摘要

具有环己烷、双环[2.2.2]辛烷或[7]三角烷骨架的刚性结构脂肪族二醛，已与对映体纯的反式-1,2-二氨基环己烷缩合，得到[3+3]或[2+2]大环化产物。与无环脂肪族亚胺不同，这些大环低聚亚胺显示出增强的稳定性，并且它们在晶体中的结构可以通过X射线衍射分析确定。对映体纯的[7]三角烷二醛在与反式-1,2-二氨基环己烷的两种对映体缩合时表现出显著的非对映选择性：只有一种对映体给出[2+2]大环化产物。圆二色性测量结合计算分析表明，这些环状低聚亚胺中能量最低的电子跃迁是n-π*型。