Use of "enantiopolar" directions in centrosymmetric crystals for direct assignment of absolute configuration of chiral molecules: application to the system serine/threonine
Use of "enantiopolar" directions in centrosymmetric crystals for direct assignment of absolute configuration of chiral molecules: application to the system serine/threonine
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使用中心对称晶体中的“对映极性”方向直接指定手性分子的绝对构型：在丝氨酸/苏氨酸系统中的应用
DOI：
10.1021/ja00371a071
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发表时间：
1982
影响因子：
15
通讯作者：
S. Weinstein
中科院分区：
文献类型：
--
作者：
L. Addadi;Z. Berkovitch;I. Weissbuch;M. Lahav;L. Leiserowitz;S. Weinstein
X射线分析不区分对映体晶体结构（7？）rf和（5）;[其中对映体分离的分子R和S堆积在相应的[} d和{j;手性晶体]中，除非应用异常分散的Bijvoet方法。另一方面，X-射线分析的中心对称晶体组成的ractobacco [7？S（明确确定了R和S部分相对于晶轴占据的位置（图1）。因此，与手性晶体相比，与R和S手性分子连接的取代基朝向所有晶面的取向是明确指定的。1然而，由于晶体中两种对映体的共存，这一知识不能直接用于手性拆分分子的绝对构型的指定。如果外消旋晶体中包含的结构信息转移到第三个手性分子上，通过明确的机制与外消旋体系立体特异性地相互作用，则可以规避这种限制。我们通过吸附溶解的“特制”杂质来抑制聚集体2和极性晶体1生长的研究，使我们了解了晶体
X-ray analysis does not distinguish between enantiomeric crystal structures (7?) rf and (5);[where theenantiomerically resolved molecules R and S pack in the corresponding [} d and {j; chiral crystal] unless theBijvoet method of anomalous dispersion is applied. On the other hand, X-ray analysis of a centrosymmetric crystal composed of a racemate [7? S (establishes unambiguously the sites occupied by the R and S moieties with respect to the crystal axes (Figure 1). Consequently, in contradistinction to chiral crystals, the orientation toward all crystal faces of the substituents attached to the R and S chiral molecules is unam-biguously assigned. 1 However, because of the coexistence of the two enantiomers in the crystals, this knowledge cannot be directly exploited for the assignment of absolute configurationof chiral resolved molecules. This limitation may be circumvented if the structural information contained in the racemic crystal is trans-ferred to a third chiral molecule, interacting stereospecifically with the racemic system through a well-defined mechanism. Our studies on inhibition of growth of conglomerates2 and polar crystals1 by adsorption of resolved “tailor-made” impurities have led to an understanding of the correlation between the crystal