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Six‐Membered Cyclic Nitroso Acetals: Synthesis and Studies of the Nitrogen Inversion Process of N ‐Silyloxy‐3,6‐dihydro‐2 H ‐1,2‐oxazines
Author(s) -
Shved Alexander S.,
Tabolin Andrey A.,
Novikov Roman A.,
Nelyubina Yulia V.,
Timofeev Vladimir P.,
Ioffe Sema L.
Publication year - 2016
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201600952
Subject(s) - chemistry , oxazines , nitroso , silylation , enol , nitrogen inversion , cycloaddition , nitroso compounds , inversion (geology) , rhodium , medicinal chemistry , computational chemistry , catalysis , organic chemistry , photochemistry , nitrogen , stereochemistry , paleontology , structural basin , biology
Silyl nitronates undergo rhodium‐catalyzed formal [3+3]‐cycloaddition with enol diazoacetates to form N ‐silyloxy‐3,6‐dihydro‐2 H ‐1,2‐oxazines. The scope of the reaction and the extent of the major side process were evaluated. A mechanistic scheme was proposed. The nitrogen inversion barrier in the obtained nitroso acetals was estimated based on both quantum calculations and kinetic measurements.