When two symmetrically independent molecules must be different: "Crystallization-induced diastereomerization" of chiral pinanyl sulfoneDedicated to the memory of Professor Evgenii Naumovich Klimovitskii, with whom we developed the original ideas which are expanded here.Electronic supplementary information (ESI) available: Selected geometrical parameters of the compounds studied by X-ray structural analysis (Table S1), DFT calculations (Table S2), experimental and calculated frequencies of the ν(

• Main Authors: Lodochnikova, Olga A, Startseva, Valeriya A, Nikitina, Liliya E, Bodrov, Andrei V, Klimovitskii, Alexander E, Klimovitskii, Evgenii N, Litvinov, Igor A
• Format: Article
• Language: English
• ISSN: 1466-8033
• DOI: 10.1039/c3ce42642d

According to X-ray data, homochiral pinanyl sulfone crystallizes as an asymmetric dimer formed by pairwise H-bonds involving stereochemically different oxygen atoms of sulfonyl groups of molecules A and B. Thus, a pro- R atom is invoked for the construction of a relevant H-bond in molecule A, but in the case of molecule B only a pro- S atom is involved. Newly formed chiral sulfur atoms take opposite chirality in molecules A and B, while the configuration of the pinane skeleton remains unchanged. Such a stereochemical transformation is called "crystallization-induced diastereomerization". The stability of the asymmetric dimer found in the crystal was evaluated within the framework of DFT (B3LYP, 6-31G (d,p)) and studied via IR spectroscopy in solution. The stereochemical transformation accompanying crystallization of homochiral pinanyl sulfone has been studied.