Chelating P2-Bis-phosphazenes with a (R,R)-1,2-Diaminocyclohexane Skeleton: Two New Chiral Superbases.

Chelating P2-Bis-phosphazenes with a (R,R)-1,2-Diaminocyclohexane Skeleton: Two New Chiral Superbases.
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DOI:
10.1002/chem.201604522
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发表时间:
2017-02
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通讯作者:
J. Kögel;B. Kovačević;Sebastian Ullrich;Xiulan Xie;J. Sundermeyer
J. Kögel;B. Kovačević;Sebastian Ullrich;Xiulan Xie;J. Sundermeyer
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文献类型:
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作者:
J. Kögel;B. Kovačević;Sebastian Ullrich;Xiulan Xie;J. Sundermeyer

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两个 P2 -磷腈基通过 C2 对称的 (R,R)-1,2-二氨基环己烷 (DACH) 主链连接产生新的手性超碱 DACH-P2 NMe2 和 DACH-P2 Pyr (Pyr=吡咯烷基)。这些碱通过基尔萨诺夫反应制备,并研究了它们的光谱和结构特征。关于其碱度性质的理论计算显示,在乙腈标度上,pKBH+ 值显着为 38.1 和 39.9;这使它们成为迄今为止已知的最强的非离子手性超强碱。
The linkage of two P2 -phosphazenyl groups through a C2 -symmetric (R,R)-1,2-diaminocyclohexane (DACH) backbone yielded the new chiral superbases DACH-P2 NMe2 and DACH-P2 Pyr (Pyr=pyrrolidinyl). These bases were prepared by a Kirsanov reaction and studied with respect to their spectroscopic and structural characteristics. Theoretical calculations concerning their basicity properties revealed remarkable pKBH+ values of 38.1 and 39.9 on the acetonitrile scale; this makes them the strongest nonionic chiral superbases known to date.