Structural Motifs in Enantiopure Halogenated Aryl Benzyl Sulfoxides: Effect of Fluorine Substitution

A series of enantiopure crystalline aryl benzyl sulfoxides, bearing different substituents on both the aryl groups, were synthesized by an enantioselective oxidation of the corresponding sulfides. Structural investigations, achieved by means of single-crystal X-ray diffraction, allowed us to recognize the main assembling interactions. The same procedure was repeated for some corresponding fluorinated aryl benzyl sulfoxides. The synthesis of the enantiomers of a new fluorinated compound, which shows unusual structural patterns, prompted us to compare the structural motifs of the two families of sulfoxides (fluorinated and unfluorinated) and to investigate the changes due to the fluorine substitution. Some short contacts involving the fluorine atom were discussed in more details, taking into account the recent interest in these sometimes controversial interactions

Stacked Naphthyls and Weak Hydrogen-Bond Interactions Govern the Conformational Behavior of <i>P</i>‑Resolved Cyclic Phosphonamides: A Combined Experimental and Computational Study

<i>P</i>-Enantiomerically pure cyclic phosphonamides have been synthesized via a cyclization reaction of (<i>S</i>,<i>S</i>)-aminobenzylnaphthols with chloromethylphosphonic dichloride. The reaction is highly stereoselective and gives almost exclusively (<i>S</i>,<i>S</i>,<i>S</i>_P)-cyclic phosphonamides in good yields. Analysis of the X-ray crystal structures shows clearly that the cyclization reaction forces the two naphthyl rings into a stable parallel displaced stacking assembly and indicates also the existence of intramolecular CH···π interactions and weak forms of intermolecular hydrogen bondings, involving the oxygen and the chlorine atoms. QM computations and NMR spectra in solution confirm the stacked molecular assembly as the preferred arrangement of the two naphthyl groups

Stacked Naphthyls and Weak Hydrogen-Bond Interactions Govern the Conformational Behavior of <i>P</i>‑Resolved Cyclic Phosphonamides: A Combined Experimental and Computational Study

<i>P</i>-Enantiomerically pure cyclic phosphonamides have been synthesized via a cyclization reaction of (<i>S</i>,<i>S</i>)-aminobenzylnaphthols with chloromethylphosphonic dichloride. The reaction is highly stereoselective and gives almost exclusively (<i>S</i>,<i>S</i>,<i>S</i>_P)-cyclic phosphonamides in good yields. Analysis of the X-ray crystal structures shows clearly that the cyclization reaction forces the two naphthyl rings into a stable parallel displaced stacking assembly and indicates also the existence of intramolecular CH···π interactions and weak forms of intermolecular hydrogen bondings, involving the oxygen and the chlorine atoms. QM computations and NMR spectra in solution confirm the stacked molecular assembly as the preferred arrangement of the two naphthyl groups

Stacked Naphthyls and Weak Hydrogen-Bond Interactions Govern the Conformational Behavior of <i>P</i>‑Resolved Cyclic Phosphonamides: A Combined Experimental and Computational Study

<i>P</i>-Enantiomerically pure cyclic phosphonamides have been synthesized via a cyclization reaction of (<i>S</i>,<i>S</i>)-aminobenzylnaphthols with chloromethylphosphonic dichloride. The reaction is highly stereoselective and gives almost exclusively (<i>S</i>,<i>S</i>,<i>S</i>_P)-cyclic phosphonamides in good yields. Analysis of the X-ray crystal structures shows clearly that the cyclization reaction forces the two naphthyl rings into a stable parallel displaced stacking assembly and indicates also the existence of intramolecular CH···π interactions and weak forms of intermolecular hydrogen bondings, involving the oxygen and the chlorine atoms. QM computations and NMR spectra in solution confirm the stacked molecular assembly as the preferred arrangement of the two naphthyl groups

Stacked Naphthyls and Weak Hydrogen-Bond Interactions Govern the Conformational Behavior of <i>P</i>‑Resolved Cyclic Phosphonamides: A Combined Experimental and Computational Study

<i>P</i>-Enantiomerically pure cyclic phosphonamides have been synthesized via a cyclization reaction of (<i>S</i>,<i>S</i>)-aminobenzylnaphthols with chloromethylphosphonic dichloride. The reaction is highly stereoselective and gives almost exclusively (<i>S</i>,<i>S</i>,<i>S</i>_P)-cyclic phosphonamides in good yields. Analysis of the X-ray crystal structures shows clearly that the cyclization reaction forces the two naphthyl rings into a stable parallel displaced stacking assembly and indicates also the existence of intramolecular CH···π interactions and weak forms of intermolecular hydrogen bondings, involving the oxygen and the chlorine atoms. QM computations and NMR spectra in solution confirm the stacked molecular assembly as the preferred arrangement of the two naphthyl groups