Study of “Racemic Compound-Like” Behavior of Diastereomeric Mixture of Pinanyl Sulfoxides by X-Ray Diffraction, IR Spectroscopy, and DFT Calculations

When two symmetrically independent molecules must be different: “Crystallization-induced diastereomerization” of chiral pinanyl sulfone

“…In a previous publication we have described the phenomenon of stable co-crystallization of diastereomeric pinanyl sulfoxides 2a and 2b, obtained by the oxidation of sulfide 1 by the use of m-chloroperbenzoic acid (Scheme 1). 17 As a minor product in this reaction, the corresponding sulfone 3 is formed, which can be also easily prepared from sulfide 1 according to a known method using hydrogen peroxide in combination with acetic acid.…”

“…1 The significantly fewer amount of Z′ = 2 structures, which are presented in the literature, are characterized by distinctions in kind between molecules A and B, which can consist of either conformation or (which is more uncommon) configuration of one or more stereogenic centers of a molecule, which are cases of co-crystallization of diastereomers. [10][11][12][13][14][15][16][17] Previously, we have discovered and studied the stable co-crystallization of diastereomeric (by a sulfur atom) pinanyl sulfoxides. 17 These compounds are crystallized as H-bonded dimers, constructed by forming a new centrosymmetrical stereogenic sulfur-containing synthon F (Fig.…”

“…[10][11][12][13][14][15][16][17] Previously, we have discovered and studied the stable co-crystallization of diastereomeric (by a sulfur atom) pinanyl sulfoxides. 17 These compounds are crystallized as H-bonded dimers, constructed by forming a new centrosymmetrical stereogenic sulfur-containing synthon F (Fig. 2).…”

Sulfur-Containing Monoterpenoids as Potential Antithrombotic Drugs: Research in the Molecular Mechanism of Coagulation Activity Using Pinanyl Sulfoxide as an Example

“…According to results of previous researches, optically active sulfoxides of the terpene series were prepared by the oxidation of the corresponding sulfides using various oxidizing agents, including m- chloroperbenzoic acid (Binns et al, 1985 ; Annunziata et al, 1987 ; Eschler et al, 1988 ; Pyne et al, 1989 ; Arai et al, 1991 ), sodium periodate (Vargas-Díaz et al, 2005 ), air oxygen (Nikitina et al, 2001 ), as well as by the Kagan-Modena and Bolm asymmetric oxidation methods (Yang et al, 1994 ; Aversa et al, 2002 ; Demakova et al, 2012a , b ). We also reported that the crystal of the diastereomer 2a might be obtained as a result of the crystallization after a careful separation of the dimer crystals (Startseva et al, 2014 ).…”

“…Previously we have ascertained a stable “racemic compound-like” behavior of diastereomeric mixture of sulfoxides 2a + 2b obtained by the oxidation of enantio-pure sulfide derivative of (–)-β-pinene (Startseva et al, 2014 ). The oxidation of a β-hydroxysulfide 1 using m- chloroperbenzoic acid resulted in the formation of the corresponding β-hydroxysulfoxide 2 as a mixture of two diastereomers in 4:5 ratio (see Scheme 1 ).…”