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Transition‐Metal Acetate‐Promoted Intramolecular Nitrene Insertion to Vinylogous Carbonates for Divergent Synthesis of Azirinobenzoxazoles and Benzoxazines
Author(s) -
Gharpure Santosh J.,
Naveen Sudi,
Samala Ganesh,
Vishwakarma Dharmendra S.
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201805493
Subject(s) - chemistry , benzoxazole , nitrene , intramolecular force , transition metal , imine , rhodium , catalysis , polymer chemistry , thermal decomposition , aryl , combinatorial chemistry , medicinal chemistry , organic chemistry , alkyl
Synthesis and isolation of highly unstable azirinobenzoxazole and benzoxazines in a chemodivergent fashion from aryl azido vinylogous carbonates by simple change in transition metal acetate is described. Thermal or rhodium(II) acetate‐mediated decomposition of these azides gave dihydroazirino benzoxazole. Their nickel(II) acetate‐promoted reaction gave 4‐dihydro‐2 H ‐benzoxazines, whereas copper(II) acetate led to the corresponding oxidized imine derivatives. Benzaoxazine derivative could be kinetically resolved using a proline‐catalyzed Mannich reaction. The benzoxazines were rapidly elaborated to angularly fused tetracyclic systems and coumarin‐fused derivatives in a “one pot” fashion.