- Preparation of zinc-homoenolate from α-sulfonyloxy ketone and bis(iodozincio)methane
-
Treatment of α-sulfonyloxy ketone with bis(iodozincio)-methane gives a zinc cyclopropoxide which is formed via a nucleophilic addition of the reagent to carbonyl group followed by an intramolecular substitution reaction. Copyright
- Nomura, Kenichi,Matsubara, Seijiro
-
-
Read Online
- Stereospecific construction of chiral tertiary and quaternary carbon by nucleophilic cyclopropanation with bis(iodozincio)methane
-
The reaction of a ketone having a leaving group at the aposition, such as a,bepoxy ketone or asulfonyloxy ketone, with bis(iodozincio) methane affords a zinc alkoxide of cyclopropanol. The reaction proceeds by nucleophilic addition of the dizinc to the carbonyl group and a sequential intramolecular nucleophilic substitution of the introduced iodozinciomethyl group to the adjacent electrophilic carbon that has a leaving group. When an optically active a,β-epoxy ketone or asulfonyloxy ketone is treated with the dizinc, a zinc alkoxide of cyclopropanol having a chiral tertiary or quaternary carbon in the cyclopropane ring is obtained, and the obtained zinc alkoxide of cyclopropanol acts as a chiral ho-moenolate. When it is treated with an electrophile in the presence of copper cyanide, it gives an optically active a-tertiary or -quaternary ketone that retains high optical purity.
- Nomura, Kenichi,Matsubara, Seijiro
-
supporting information; experimental part
p. 147 - 152
(2010/04/23)
-