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Generation of Nucleophilic Chromium Acetylides From gem-Trichloroalkanes and Chromium Chloride: Synthesis of Propargyl Alcohols

Generation of Nucleophilic Chromium Acetylides From gem-Trichloroalkanes and Chromium Chloride: Synthesis of Propargyl Alcohols

Dhurke Kashinath, Steve Tisserand, Narender Puli, John R Falck, Rachid Baati

European J Org Chem. 2010 Apr 1;2010(10):1869-1874.

PMID: 21562621

Abstract:

Nucleophilic mixed chromium(II) and chromium(III) acetylides are generated from the smooth reduction of primary 1,1,1-trichloroalkanes with chromium(II) chloride in the presence of an excess amount of triethylamine at room temperature. These species arise from chromium(III) vinylidene carbenoids. It has been demonstrated that uncommon low-valent Cr(II) acetylides are formed by C-H insertion of Cr(II)Cl(2) into terminal alkynes, formed in situ through the Fritsch- Buttenberg-Wiechell (FBW) rearrangement, whereas Cr(III) acetylides are concomitantly generated by HCl elimination from the chromium(III) vinylidene carbenoid. Both divergent pathways result, overall, in the formation of nucleophilic acetylides. In situ trapping with electrophilic aldehydes afforded propargyl alcohols. Furthermore, deuteration experiments and the use of deuterium labeled 1,1,1-trichloroalkane substrates demonstrated the prevalence of low-valent Cr(II) acetylides, potentially useful, yet highly elusive synthetic intermediates.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP10049055	Chromium(II) chloride		10049-05-5	Price

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