Data for all-Oxygen Carbon Stereocenters: Synthesis, Enantiomeric Stability, Resolution and Absolute Configuration

Stereogenic atoms represent one of the most fundamental forms of molecular chirality. Despite decades of research, certain atomic assemblies remain unknown as single enantiomers, such as tetra heterosubstituted methanes. Herein, a one-step strategy to chiral all-oxygen spiro adducts is reported. Using enantioselective dynamic chromatography, a remarkable barrier of enantiomerization is determined (DeltaG‡298 up to 27.6 kcal/mol). Single enantiomers are afforded by chiral stationary phase high-performance liquid chromatography. A cryptochiral character (gabs ~10-5) is revealed by electronic circular dichroism analysis affording nevertheless robust absolute configuration assignment by TDDFT calculations. Crystalline diastereomeric structures made from rigid pinane skeletons confirm the structural and configurational assignments. Our study highlights that tetraoxa carbon (stereo)centers are readily made and isolated, and constitute possible targets for new (asymmetric) functional group manipulations.

Organizational unit

Laboratory of Professor Jérôme Lacour

Type

Dataset

DOI

10.26037/yareta:uaqqxl3mzvhotoihpqbruxieda

License

Creative Commons Attribution 4.0 International