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On the reduction of tertiary radicals by samarium diiodide (SmI<inf>2</inf>)

Nagashima, T and Rivkin, A and Curran, DP (2000) On the reduction of tertiary radicals by samarium diiodide (SmI<inf>2</inf>). Canadian Journal of Chemistry, 78 (6). 791 - 799. ISSN 0008-4042

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Abstract

Reduction of o-iodophenyl 3-methylbut-2-enyl ether with samarium diiodide generates mixtures of 3-isopropyl-2,3-dihydrobenzofuran and 3-(2-propenyl)-2,3-dihydrobenzofuran along with a small amount of dimer. If a source of deuterium is present during the reduction, then the 3-isopropyl product predominates and this product is labeled with one deuterium. However, attempts to quench the putative tertiary organosamarium reagent by adding a deuterium source after the reduction were not very successful at room temperature. But at 0°C, the organosamarium reagent was generated (at least to the extent of about 50%, as measured by deuterium quenching), and its decomposition was followed over time by a series of quenching experiments. The results suggest that tertiary radicals are reduced to a significant extent by SmI2 to form an anionic (presumably alkylsamarium) species. This species is thermally unstable and decomposes to the corresponding reduced and eliminated products. The reduced product is consistently formed in slight excess over the eliminated one, and the mechanism of formation of these products is not yet clear.


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Details

Item Type: Article
Status: Published
Creators/Authors:
CreatorsEmailPitt UsernameORCID
Nagashima, T
Rivkin, A
Curran, DPcurran@pitt.eduCURRAN
Date: 1 January 2000
Date Type: Publication
Journal or Publication Title: Canadian Journal of Chemistry
Volume: 78
Number: 6
Page Range: 791 - 799
DOI or Unique Handle: 10.1139/v00-011
Schools and Programs: Dietrich School of Arts and Sciences > Chemistry
Refereed: Yes
ISSN: 0008-4042
Date Deposited: 25 Feb 2014 15:35
Last Modified: 03 Aug 2019 14:55
URI: http://d-scholarship.pitt.edu/id/eprint/20632

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