Nitrene‐Mediated C−H Oxygenation: Catalytic Enantioselective Formation of Five‐Membered Cyclic Organic Carbonates

The synthesis of non-racemic 5-membered cyclic carbonates from abundant alcohols is reported. Conversion the alcohol into an azanyl carbonate followed by a chiral-at-ruthenium catalyzed cyclization to provide chiral in yields up 95% and with 99% ee. This new synthetic method proposed proceed through nitrene-mediated intramolecular C(sp 3 )−H oxygenation which includes very unusual 1,7-hydrogen atom transfer within ruthenium nitrenoid intermediate. applicable mono-, di- trisubstituted alkylene carbonates.