Sequential Carbon–Carbon/Carbon–Selenium Bond Formation Mediated by Iron(III) Chloride and Diorganyl Diselenides: Synthesis and Reactivity of 2‑Organoselenyl-Naphthalenes

In this paper, we report an intramolecular cyclization of benzylic-substituted propargyl alcohols promoted by iron­(III) chloride and diorganyl diselenides to give 2-organoselenyl-naphthalenes via a sequential carbon–carbon/carbon–selenium bond formation. The present reaction tolerated a wide range...

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Bibliographic Details
Published inJournal of organic chemistry Vol. 82; no. 5; pp. 2713 - 2723
Main Authors Recchi, Ana M. S, Back, Davi F, Zeni, Gilson
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 03.03.2017
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Organic
Physical Sciences
Science & Technology
NAPHTHALENE DERIVATIVES
ELECTROPHILIC CYCLIZATION
ROOM-TEMPERATURE
DIARYL CHALCOGENIDES
COPPER-CATALYZED SYNTHESIS
COUPLING REACTIONS
DIPHENYL DISELENIDE
GLUTATHIONE-PEROXIDASE
SE-SE
ARYLBORONIC ACIDS
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Summary:In this paper, we report an intramolecular cyclization of benzylic-substituted propargyl alcohols promoted by iron­(III) chloride and diorganyl diselenides to give 2-organoselenyl-naphthalenes via a sequential carbon–carbon/carbon–selenium bond formation. The present reaction tolerated a wide range of substituents in both propargyl alcohols and diorganyl diselenides to give the desired 2-organoselenyl-naphthalenes in good yields with high selectivity. In addition, O-acyl protected propargyl alcohol and propargyl bromide were also subjected to this protocol giving the corresponding 2-organoselenyl-naphthalenes. We found that dichalcogenide species affected the formation of cyclized products, whereas diorganyl diselenides gave high yields, moderate yields were obtained with diorganyl disulfides, and no product formation was found with diorganyl ditellurides. The key transformations could be attributed to the carbon–carbon triple bond activation of benzylic-substituted propargyl alcohols by a seleniranium ion, antiattack of the electron cloud from the aromatic ring at the activated triple bond, and cyclization via an exclusive 6-endo-dig process. We also found that the corresponding 2-organoselenyl-naphthalenes are suitable substrates to the selenium–lithium exchange reactions followed by trapping with aldehydes affording the corresponding secondary alcohols.
ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.7b00050