Electron transfer photochemistry of chrysanthemol: An intramolecular S(N)2' reaction of a vinylcyclopropane radical cation

被引:31
作者
Herbertz, T [1 ]
Roth, HD [1 ]
机构
[1] RUTGERS STATE UNIV, DEPT CHEM, WRIGHT RIEMAN LABS, NEW BRUNSWICK, NJ 08855 USA
关键词
D O I
10.1021/ja953596c
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The electron transfer photochemistry of optically pure (1R,3S)-(f)-cis-chrysanthemol (cis-2) results in the formation of (R)-5-(1-(p-cyanophenyl)-1-methyethyl)-2,2-dimethyl oxacyclohex-3-ene (4) with significant retention of optical activity. The product is rationalized via nucleophilic attack of the alcoholic function of the radical cation on the terminal carbon of the vinyl group with simultaneous replacement of an isopropyl radical as an intramolecular leaving group in an apparent S(N)2' reaction. This mode of attack is unprecedented in vinylcyclopropane radical cations and is interpreted as evidence for the significant role that relief of ring strain and its avoidance play in determining the course of nucleophilic capture in radical cationic systems.
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页码:10954 / 10962
页数:9
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