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Nitrene-Mediated C-H Oxygenation: Catalytic Enantioselective Formation of Five-Membered Cyclic Organic Carbonates
Xin Nie1, Chen-Xi Ye1, Sergei I Ivlev1
1Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35043, Marburg, Germany.
Abstract:
The synthesis of non-racemic 5-membered cyclic carbonates from abundant alcohols is reported. Conversion of the alcohol into an azanyl carbonate is followed by a chiral-at-ruthenium catalyzed cyclization to provide chiral cyclic carbonates in yields of up to 95 % and with up to 99 % ee. This new synthetic method is proposed to proceed through a nitrene-mediated intramolecular C(sp3 )-H oxygenation which includes an unusual 1,7-hydrogen atom transfer within a ruthenium nitrene intermediate. The method is applicable to the synthesis of non-racemic chiral mono-, di- and trisubstituted cyclic alkylene carbonates.
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