Enantiopure O-substituted phenylphosphonothioic acids:: Chiral recognition ability during salt crystallization and chiral recognition mechanism
Enantiopure O-substituted phenylphosphonothioic acids:: Chiral recognition ability during salt crystallization and chiral recognition mechanism
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DOI：
10.1021/jo052020v
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发表时间：
2006-01-20
影响因子：
3.6
通讯作者：
Saigo, K
中科院分区：
文献类型：
--
作者：
Kobayashi, Y;Morisawa, F;Saigo, K
研究了对映纯的o -甲基、o -乙基、o -丙基和o -苯基苯基膦硫酸（1a-d）在盐结晶过程中对各种外消旋胺的手性识别能力及手性识别机理。对映物1a-d对多种外消旋胺的手性识别能力在6 ~ 99%的对映体选择性范围内变化。沉积的难溶非对映体盐分为棱柱型和针状两类；棱柱型晶体由球状分子簇组成，针状晶体则由21柱组成。与一般观察到的手性伯胺与手性羧酸的非对映体盐晶体中类似的21柱相反，球状分子簇是一个非常独特的氢键基序，从未在非对映体盐晶体中构建过。当难溶非对映异构体盐为棱柱型晶体时，手性识别效果良好。发现手性识别程度与α -d、难溶非对映异构体盐的晶体形状和氢键基序（分子簇/2(1)列）之间存在显著相关性。在x射线晶体学分析的基础上，详细讨论了分子簇和21柱形成的手性识别机制。
The chiral recognition ability of enantiopure O-methyl, O-ethyl, O-propyl, and O-phenyl phenylphosphonothioic acids (1a-d) for various kinds of racemic amines during salt crystallization and the chiral recognition mechanism were thoroughly investigated. The chiral recognition abilities of enantiopure 1a-d for a wide variety of racemic amines varied in a range of 6 to > 99% enantiomeric selectivity. Deposited less-soluble diastereomeric salts were classified into two categories, prism- and needle-type crystals; the prism-type crystals were composed of a globular molecular cluster, while there existed a 21 column in the needle-type crystals. In contrast to a general observation of a similar 21 column in the less-soluble diastereomeric salt crystals of chiral primary amines with chiral carboxylic acids, the globular molecular cluster is a very unique hydrogen-bonding motif that has never been constructed in diastereomeric salt crystals. Excellent chiral recognition was always achieved when the less-soluble diastereomeric salts were prism-type crystals. Significant correlations were found between the degree of the chiral recognition with 1a-d, the crystal shape of the less-soluble diastereomeric salts, and the hydrogen-bonding motif (molecular cluster/2(1) column). The chiral recognition mechanisms via the molecular cluster and the 21 column formations are discussed in detail on the basis of X-ray crystallographic analyses.