Solvent-dependent self-discrimination of bis(2-hydroxyphenyl)diamides.
Solvent-dependent self-discrimination of bis(2-hydroxyphenyl)diamides.
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DOI：
10.1002/chem.201000321
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发表时间：
2010-05
期刊：
影响因子：
--
通讯作者：
Akinobu Matsuzawa;Akihiro Nojiri;N. Kumagai;M. Shibasaki
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文献类型：
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作者：
Akinobu Matsuzawa;Akihiro Nojiri;N. Kumagai;M. Shibasaki
Solvent-dependent, self-discrimination of diamides is described. Mixing a solution of (R)-1a and (S)-1a, which are valine-derived, bis(2-hydroxyphenyl)diamide-bearing, multiple hydrogen-bonding modules, in dichloromethane immediately led to the formation of a thick suspension comprising a 1:1 heterochiral aggregate of 1a. The solubility of heterochiral 1a was substantially lower in halogenated solvents than in ethyl acetate. A perusal of racemic crystal structures obtained from chloroform and ethyl acetate revealed a significant difference in the crystal-packing pattern, which is likely to be the basis for the pronounced difference in solubility. Specific self-discrimination of 1 a in an ensemble of eight structurally related molecules showcased the specific aggregation through the hydrogen-bonding network of the bis(2-hydroxyphenyl)diamide framework. The low solubility of heterochiral 1a in halogenated solvent was exploited to achieve high stereoselectivity in a catalytic asymmetric reaction by using a low enantiomeric excess sample of 1a.
