jo8b01652_si_002.cif (422.97 kB)
Acylation of Nitronates: [3,3]-Sigmatropic Rearrangement of in Situ Generated N‑Acyloxy,N‑oxyenamines
dataset
posted on 2018-08-01, 00:00 authored by Aleksandr
O. Kokuev, Yulia A. Antonova, Valentin S. Dorokhov, Ivan S. Golovanov, Yulia V. Nelyubina, Andrey A. Tabolin, Alexey Yu. Sukhorukov, Sema L. IoffeAcylation
of nitronates affords α-acyloxyoxime derivatives
via an umpolung functionalization of the α-position. This transformation
involves generation of hitherto unknown N-acyloxy,N-oxyenamines and their fast [3,3]-sigmatropic
rearrangement driven by the cleavage of the weak N–O bond.
The reaction has a broad scope, and it is regioselective in the case
of nitronates possessing nonsymmetrically substituted α-positions.
Application to the formal total synthesis of clausenamide and cis-clausenamide is presented.
