Iodine atom transfer [3 + 2] cycloaddition reaction with electron-rich alkenes using N-tosyliodoaziridine derivatives as novel azahomoallyl radical precursors

Osamu Kitagawa, Shinsaku Miyaji, Yoichiro Yamada, Hiroki Fujiwara, Takeo Taguchi

Research output: Contribution to journalArticle

27 Citations (Scopus)

Abstract

Treatment of N-tosyliodoaziridine derivatives with Et3B efficiently produces various azahomoallyl radical (2-akenylamidyl radical) species which give oxygen-functionalized pyrrolidine derivatives through iodine atom transfer [3 + 2] cycloaddition with electron-rich alkenes such as enol ethers and ketene acetal. The present cycloaddition reaction proceeds regioselectively via C-N bond cleavage of an aziridinylalkyl radical intermediate and addition of the resulting azahomoallyl radicals to the terminal carbon of an alkene. The reaction of alkenes with the cyclohexenylamidyl radical generated from an optically active bicyclic iodoaziridine [(1S,2S,6S)-2-iodo-7-(p-toluenesulfonyl)-7-azabicyclo[4.1.0]heptane, 94% eel also proceeds to give optically active octahydroindole derivatives (84-93% ee).

Original languageEnglish
Pages (from-to)3184-3189
Number of pages6
JournalJournal of Organic Chemistry
Volume68
Issue number8
DOIs
Publication statusPublished - 2003 Apr 18
Externally publishedYes

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Cycloaddition
Alkenes
Iodine
Derivatives
Atoms
Electrons
Heptanes
Acetals
Ethers
Carbon
Oxygen

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Iodine atom transfer [3 + 2] cycloaddition reaction with electron-rich alkenes using N-tosyliodoaziridine derivatives as novel azahomoallyl radical precursors. / Kitagawa, Osamu; Miyaji, Shinsaku; Yamada, Yoichiro; Fujiwara, Hiroki; Taguchi, Takeo.

In: Journal of Organic Chemistry, Vol. 68, No. 8, 18.04.2003, p. 3184-3189.

Research output: Contribution to journalArticle

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abstract = "Treatment of N-tosyliodoaziridine derivatives with Et3B efficiently produces various azahomoallyl radical (2-akenylamidyl radical) species which give oxygen-functionalized pyrrolidine derivatives through iodine atom transfer [3 + 2] cycloaddition with electron-rich alkenes such as enol ethers and ketene acetal. The present cycloaddition reaction proceeds regioselectively via C-N bond cleavage of an aziridinylalkyl radical intermediate and addition of the resulting azahomoallyl radicals to the terminal carbon of an alkene. The reaction of alkenes with the cyclohexenylamidyl radical generated from an optically active bicyclic iodoaziridine [(1S,2S,6S)-2-iodo-7-(p-toluenesulfonyl)-7-azabicyclo[4.1.0]heptane, 94{\%} eel also proceeds to give optically active octahydroindole derivatives (84-93{\%} ee).",
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