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Synlett 2010(18): 2717-2720  
DOI: 10.1055/s-0030-1258813
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

TBAF-Promoted Dehydrobrominations of Vicinal Dibromides Having an Adjacent O-Functional Group

Noriki Kutsumura*, Keisuke Kubokawa, Takao Saito*
Department of Chemistry, Faculty of Science, Tokyo University of Science, Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan
Fax: +81(3)52614631; e-Mail: nkutsu@rs.kagu.tus.ac.jp; e-Mail: tsaito@rs.kagu.tus.ac.jp;
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Publication History

Received 23 August 2010
Publication Date:
08 October 2010 (online)

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Abstract

Regioselective HBr elimination of vicinal dibromides having an adjacent oxygen functional group to give the corresponding 2-bromoalk-1-enes was controlled using 1.1 equivalents of TBAF. Two-step elimination to give the corresponding alkynes was controlled using 5.0 equivalents of TBAF. High yield and high selectivity require the presence of an oxygen functional group at the neighboring position of the elimination site.

Key words

elimination - 2-bromoalk-1-enes - alkynes - TBAF - vicinal dibromides

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13

General Procedures for the Syntheses of 2-Bromoalk-1-ene 1 and Alkyne 2
A mixture of 1,2-dibromoalkane 3 (1.0 equiv) and TBAF (1 M in THF solution, 1.1 equiv or 5.0 equiv) in DMF (0.1 M) was stirred at 60 ˚C. The reaction was quenched with sat. aq NH4Cl, and the reaction mixture was extracted with EtOAc, concentrated in vacuo, and purified by silica gel column chromatography to afford 1 or 2.