Synthesis of Spiro[2.2]pentanes and Spiro[2.3]hexanes Employing the Me3Al/CH2I2 Reagent

Synthesis of Spiro[2.2]pentanes and Spiro[2.3]hexanes Employing the Me3Al/CH2I2 Reagent

Substituted alkylidenecyclopropanes reacted with 5 equivalents each of Me3Al and CH2I2 at room temperature in hexane to give 1‐mono‐ and 1,1‐disubstituted spiro[2.2]pentanes in high yields. Surprisingly, the same reaction with substituted alkylidenecyclopropanes in CH2Cl2 afforded exclusively 1,1‐di...

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Veröffentlicht in:European journal of organic chemistry 2017-12, Vol.2017 (47), p.7060-7067
Hauptverfasser: Ramazanov, Ilfir R., Kadikova, Rita N., Zosim, Tat'yana P., Dzhemilev, Usein M., de Meijere, Armin
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Aluminum
Carbenoids
Cyclopropanation
Hexanes
Pentanes
Small ring systems
Spiro compounds
Substitutes
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container_end_page 7067
container_issue 47
container_start_page 7060
container_title European journal of organic chemistry
container_volume 2017
creator Ramazanov, Ilfir R.
Kadikova, Rita N.
Zosim, Tat'yana P.
Dzhemilev, Usein M.
de Meijere, Armin
description Substituted alkylidenecyclopropanes reacted with 5 equivalents each of Me3Al and CH2I2 at room temperature in hexane to give 1‐mono‐ and 1,1‐disubstituted spiro[2.2]pentanes in high yields. Surprisingly, the same reaction with substituted alkylidenecyclopropanes in CH2Cl2 afforded exclusively 1,1‐disubstituted spiro[2.3]hexanes. The transformation of 1,1‐diphenylspiro[2.2]pentane into 1,1‐diphenylspiro[2.3]hexane was studied with the use of CD2I2 and a plausible mechanism was suggested. The reaction of substituted alkylidenecyclobutanes with the Me3Al/CH2I2 reagent in CH2Cl2 gave only 1,1‐disubstituted spiro[2.3]hexanes. Alkylidene‐cyclopropanes and ‐cyclobutanes with Me3Al/CH2I2 reagent in hexane gave substituted spiro[2.2]‐pentanes and ‐hexanes in high yields. The reaction with alkylidenecyclopropanes in CH2Cl2 afforded exclusively 1,1‐disubstituted spiro[2.3]hexanes. The transformation of 1,1‐diphenylspiro[2.2]pentane into 1,1‐diphenylspiro[2.3]hexane was studied with CD2I2, and a mechanism was suggested.
doi_str_mv 10.1002/ejoc.201700991
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source Wiley Online Library Journals Frontfile Complete
subjects Aluminum
Carbenoids
Cyclopropanation
Hexanes
Pentanes
Small ring systems
Spiro compounds
Substitutes
title Synthesis of Spiro[2.2]pentanes and Spiro[2.3]hexanes Employing the Me3Al/CH2I2 Reagent
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