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Fluoride-Assisted Activation of Calcium Carbide: A Simple Method for the Ethynylation of Aldehydes and Ketones

Abolfazl HosseiniInstitute of Organic Chemistry, Justus-Liebig University, Heinrich-Buff-Ring 58, 35392 Giessen, GermanyDaniel SeidelDepartment of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, Piscataway, New Jersey 08854, United StatesAndreas MiskaInstitute of Inorganic and Analytical Chemistry, Justus-Liebig University, Heinrich-Buff-Ring 58, 35392 Giessen, GermanyPeter R. SchreinerInstitute of Organic Chemistry, Justus-Liebig University, Heinrich-Buff-Ring 58, 35392 Giessen, Germany
2015en
ABI

Аннотация

The fluoride-assisted ethynylation of ketones and aldehydes is described using commercially available calcium carbide with typically 5 mol % of TBAF·3H2O as the catalyst in DMSO. Activation of calcium carbide by fluoride is thought to generate an acetylide "ate"-complex that readily adds to carbonyl groups. Aliphatic aldehydes and ketones generally provide high yields, whereas aromatic carbonyls afford propargylic alcohols with moderate to good yields. The use of calcium carbide as a safe acetylide ion source along with economic amounts of TBAF·3H2O make this procedure a cheap and operationally simple method for the preparation of propargylic alcohols.

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