Racemic Tartrate/Malate Anions Combine with Racemic Complex Cations to Form Optically Active Ionic Crystals
Racemic Tartrate/Malate Anions Combine with Racemic Complex Cations to Form Optically Active Ionic Crystals
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外消旋酒石酸根/苹果酸根阴离子与外消旋复合阳离子结合形成光学活性离子晶体
DOI：
10.1002/chem.202100576
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发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Konno Takumi
中科院分区：
文献类型：
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作者：
Uno Masashi;Kojima Tatsuhiro;Kuwamura Naoto;Yoshinari Nobuto;Konno Takumi
自巴斯德对外消旋酒石酸盐结晶行为的研究以来，自发分解一直受到各个研究领域的关注。本文报道了这一现象的一个独特的例子，涉及消旋型rr /SS‐酒石酸盐或r /S‐苹果酸盐和消旋型ΔΔ/ΛΛ‐[Ag3Rh2（2‐氨基乙烷乙硫酸酯）6]3+（ΔΔ/ΛΛ‐[1]3+）在水中产生的离子晶体。RR‐和SS‐酒石酸盐选择性地识别bbb3 +的ΛΛ和ΔΔ异构体，分别产生（ΛΛ‐[1]）2（RR‐酒石酸盐）3和（ΔΔ‐[1]）2（SS‐酒石酸盐）3的离子晶体，可以进行自发分解。当使用R/S -苹果酸盐时也会发生自发分解，R - and -苹果酸盐选择bbb3 +的相反异构体，分别得到（ΔΔ‐[1]）2（R‐苹果酸盐）3和（ΛΛ‐[1]）2（S‐苹果酸盐）3的离子晶体。在S -天冬氨酸存在下，（ΛΛ‐[1]）2（R‐酒石酸盐）3和（ΔΔ‐[1]）2（S‐酒石酸盐）3分别在溶液pH值为6和10时优先从ΔΔ/ΛΛ‐bbb3 +和rr /SS‐酒石酸盐中结晶。这一发现为化学物质的自发分辨和自然界中同手性的起源提供了重要的见解。
Spontaneous resolution has attracted continuing attention in various research fields since Pasteur's work on the crystallization behavior of racemic tartrate. Here, a unique example of this phenomenon is reported, involving ionic crystals generated from racemicRR/SS‐ tartrate orR/S‐malate and racemic ΔΔ/ΛΛ‐[Ag3Rh2(2‐aminoethanethiolato)6]3+(ΔΔ/ΛΛ‐[1]3+) in water.RR‐ andSS‐tartrate selectively recognize the ΛΛ and ΔΔ isomers of [1]3+to produce ionic crystals of (ΛΛ‐[1])2(RR‐tartrate)3and (ΔΔ‐[1])2(SS‐tartrate)3, respectively, which can undergo spontaneous resolution. While spontaneous resolution also occurs when usingR/S‐malate,R‐ andS‐malate select the opposite isomers of [1]3+to give ionic crystals of (ΔΔ‐[1])2(R‐malate)3and (ΛΛ‐[1])2(S‐malate)3, respectively. In the presence ofS‐aspartate, (ΛΛ‐[1])2(R‐tartrate)3and (ΔΔ‐[1])2(S‐tartrate)3are preferentially crystallized from ΔΔ/ΛΛ‐[1]3+andRR/SS‐tartrate at solution pH values of 6 and 10, respectively. This finding provides significant insight into the optical resolution of chemical species by spontaneous resolution and the origin of homochirality in nature.