Generation of cycloalkynes by hydro-iodonio-elimination of vinyl iodonium salts.
Generation of cycloalkynes by hydro-iodonio-elimination of vinyl iodonium salts.
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DOI：
10.1021/ar040293r
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发表时间：
2005-05
影响因子：
18.3
通讯作者：
T. Okuyama;Morifumi Fujita
中科院分区：
文献类型：
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作者：
T. Okuyama;Morifumi Fujita
1-环己烯基碘盐与乙酸酯或其他碱通过E2和E1机制可以有效地生成环己炔。观察到的取代环己炔的亲核加成反应的区域选择性符合LUMO布居：变形越小的乙炔碳越亲电。环己亚甲基碘盐在很弱的碱性条件下，经1，2-重排反应生成环庚炔。
Cyclohexynes can be generated efficiently from 1-cyclohexenyliodonium salts with acetate or other bases via the E2 and E1 mechanism. The observed regioselectivity of nucleophilic addition to substituted cyclohexynes conforms to the LUMO populations: the less deformed acetylenic carbon is more electrophilic. Cycloheptyne can form by the E1-type elimination via 1,2-rearrangement from cyclohexylidenemethyliodonium salt under very weakly basic conditions.