The hypervalent iodine oxidation of phenol derivatives bearing
aminoquinones at the ortho (9) or
meta positions (19) in 2,2,2-trifluoroethanol was
investigated with the aim of preparing novel
antitumor compounds. Azacarbocyclic spirodienone derivatives
(13) or phenol derivatives containing
the 2,3-dihydro-1H-azepine systems (17,
20) were selectively obtained by the reaction of these
phenol
derivatives and the hypervalent iodine reagent, phenyliodine(III)
bis(trifluoroacetate). The
application of this reaction to phenol derivatives bearing
aminoquinones (10−12) is also
described.
The rearrangement reaction of α,β-epoxy acylates in
cyclic systems was studied. The treatment of
cis-derivatives with a Lewis acid afforded rearranged
products via the regioselective β-cleavage of
the oxirane ring due to the electron-withdrawing nature of the acyloxy
group, whereas trans-derivatives enhanced the neighboring group participation to yield only a
small amount of rearranged
products. This rearrangement reaction proved to be useful for the
construction of a variety of
spirocyclane systems or quaternary carbon centers on rings and could be
applied to their syntheses
as optically active forms.
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