Dataset for all-Heteroatom-Substituted Carbon Spiro Stereocenters: Synthesis, Resolution, Enantiomeric Stability, and Absolute Configuration

Chiral tetra heterosubstituted methanes, i.e. tetraoxa and azatrioxa carbon spiro stereocenters, are synthesized in one-step under CpRu catalysis, using cyclic carbonates and carbamates as substrates and alpha-diazo-beta-ketoesters as reagents. Single enantiomers, isolated by chiral stationary phase chromatography, display chiroptical properties, from gabs ~10–5 to ~10–4, which, together with TD-DFT calculations, provide robust absolute configuration assignments. Crystalline spiro diastere-omers were also obtained, confirming further the structural and configurational assignments. Using enantioselective dy-namic chromatography, remarkable enantiomerization barriers were determined for the ortho-carbonates and ortho-carbamates, with values up to 27.6 and 34.6 kcal/mol (half-lives 227 days and >84’000 years at 25 °C, respec-tively). DFT further elucidates the origin of this large differ-ence pointing towards preferred C-O or C-N bond cleavages in the rate-determining step of the SN1-like mechanism.

Organizational unit

Laboratory of Professor Jérôme Lacour

Type

Dataset

DOI

10.26037/yareta:26l4n6rn5bgovfx45rlfedw4ou

License

Creative Commons Attribution 4.0 International