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

Araki Masuyama; Tomohiro Sugawara; Masatomo Nojima; Kevin J. McCullough

doi:10.1016/S0040-4020(02)01522-3

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

Araki Masuyama, Tomohiro Sugawara, Masatomo Nojima, Kevin J. McCullough

School of Engineering & Physical Sciences

Research output: Contribution to journal › Article › peer-review

15 Citations (Scopus)

Abstract

Treatment of 1-methyl-2-methylene-1-cyclohexyl hydroperoxide with a mixture of FeSO₄/CuCl₂ 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 FeSO₄/CuCl₂ or with FeSO₄ only. The influence of substituents on the efficiency of the 8-endo-trig cyclization process was also explored. © 2003 Published by Elsevier Science Ltd.

Original language	English
Pages (from-to)	353-366
Number of pages	14
Journal	Tetrahedron
Volume	59
Issue number	3
DOIs	https://doi.org/10.1016/S0040-4020(02)01522-3
Publication status	Published - 13 Jan 2003

Keywords

Allylic hydroperoxide
endo-trig radical cyclization
Iron(II) sulfate
Ring enlargement

Access to Document

10.1016/S0040-4020(02)01522-3

Cite this

@article{28e1ceeaf4bf40e5a7124c2c9921594d,

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

abstract = "Treatment of 1-methyl-2-methylene-1-cyclohexyl hydroperoxide with a mixture of FeSO4/CuCl2 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 FeSO4/CuCl2 or with FeSO4 only. The influence of substituents on the efficiency of the 8-endo-trig cyclization process was also explored. {\textcopyright} 2003 Published by Elsevier Science Ltd.",

keywords = "Allylic hydroperoxide, endo-trig radical cyclization, Iron(II) sulfate, Ring enlargement",

author = "Araki Masuyama and Tomohiro Sugawara and Masatomo Nojima and McCullough, {Kevin J.}",

year = "2003",

month = jan,

day = "13",

doi = "10.1016/S0040-4020(02)01522-3",

language = "English",

volume = "59",

pages = "353--366",

journal = "Tetrahedron",

issn = "0040-4020",

publisher = "Elsevier",

number = "3",

}

TY - JOUR

T1 - Regioselective radical cyclization initiated by the reaction of allylic hydroperoxides with iron(II) sulfate

AU - Masuyama, Araki

AU - Sugawara, Tomohiro

AU - Nojima, Masatomo

AU - McCullough, Kevin J.

PY - 2003/1/13

Y1 - 2003/1/13

N2 - Treatment of 1-methyl-2-methylene-1-cyclohexyl hydroperoxide with a mixture of FeSO4/CuCl2 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 FeSO4/CuCl2 or with FeSO4 only. The influence of substituents on the efficiency of the 8-endo-trig cyclization process was also explored. © 2003 Published by Elsevier Science Ltd.

AB - Treatment of 1-methyl-2-methylene-1-cyclohexyl hydroperoxide with a mixture of FeSO4/CuCl2 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 FeSO4/CuCl2 or with FeSO4 only. The influence of substituents on the efficiency of the 8-endo-trig cyclization process was also explored. © 2003 Published by Elsevier Science Ltd.

KW - Allylic hydroperoxide

KW - endo-trig radical cyclization

KW - Iron(II) sulfate

KW - Ring enlargement

UR - http://www.scopus.com/inward/record.url?scp=0037434002&partnerID=8YFLogxK

U2 - 10.1016/S0040-4020(02)01522-3

DO - 10.1016/S0040-4020(02)01522-3

M3 - Article

SN - 0040-4020

VL - 59

SP - 353

EP - 366

JO - Tetrahedron

JF - Tetrahedron

IS - 3

ER -

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

Abstract

Keywords

Access to Document

Other files and links

Fingerprint

Cite this