Regioselective radical cyclization initiated by the reaction of allylic hydroperoxides with iron(II) sulfate

Treatment of 1-methyl-2-methylene-1-cyclohexyl hydroperoxide with a mixture of FeSO 4/CuCl 2 yielded 1-(1-chlorocyclohexyl)ethanone as the major product consistent with 6- endo- trig cyclization of the intermediate 5-acetylhex-5-enyl radical. This strategy was extended to the ring enlargement of a s...

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Bibliographic Details
Published in:Tetrahedron 2003-01, Vol.59 (3), p.353-366
Main Authors: Masuyama, Araki, Sugawara, Tomohiro, Nojima, Masatomo, McCullough, Kevin J
Format: Article
Language:English
Subjects:
allylic hydroperoxide
endo- trig radical cyclization
iron(II) sulfate
ring enlargement
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Summary:Treatment of 1-methyl-2-methylene-1-cyclohexyl hydroperoxide with a mixture of FeSO 4/CuCl 2 yielded 1-(1-chlorocyclohexyl)ethanone as the major product consistent with 6- endo- trig cyclization of the intermediate 5-acetylhex-5-enyl radical. This strategy was extended to the ring enlargement of a series of 1-isopropenylcycloalkyl hydroperoxides. Regioselective 7- or 8- endo- trig cyclization reactions could be achieved by treatment of the corresponding cyclopentyl or cyclohexyl hydroperoxides with either a mixture of FeSO 4/CuCl 2 or with FeSO 4 only. The influence of substituents on the efficiency of the 8- endo- trig cyclization process was also explored. Graphic
ISSN:0040-4020
1464-5416
DOI:10.1016/S0040-4020(02)01522-3