Nonconcerted Cycloaddition
of 2<i>H</i>-Azirines to Acylketenes: A Route to N-Bridgehead
Heterocycles
Alexander F. Khlebnikov
Mikhail
S. Novikov
Viktoriia V. Pakalnis
Dmitry S. Yufit
10.1021/jo201563b.s001
https://acs.figshare.com/articles/dataset/Nonconcerted_Cycloaddition_of_2_i_H_i_Azirines_to_Acylketenes_A_Route_to_N_Bridgehead_Heterocycles/2582020
Reactions of acylketenes, generated from diazo diketones,
with
2-unsubstituted and 2-monosubstituted 3-aryl-2<i>H</i>-azirines
lead to 1:1 or 2:1 adducts, which are derivatives of 5-oxa-1-azabicyclo[4.1.0]hept-3-ene
or 5,7-dioxa-1-azabicyclo[4.4.1]undeca-3,8-diene. According to DFT
B3LYP/6-31G(d) computations, the formation of (4+2)-monoadducts proceeds
via a stepwise non-pericyclic mechanism. Reaction with methanol transforms
quantitatively both 1:1 and 2:1 adducts into 1,4-oxazepine derivatives.
2016-02-22 14:30:23
adduct
monosubstituted
dioxa
DFT B 3LYP computations
monoadduct
proceed
mechanism
methanol
aryl
Acylketene
derivative
oxazepine
HeterocyclesReaction
Nonconcerted Cycloaddition
oxa
diazo diketones
unsubstituted
acylketene
formation