ChemInform Abstract: Generation of Nucleophilic Chromium Acetylides from gem-Trichloroalkanes and Chromium Chloride: Synthesis of Propargyl Alcohols

Autor:	John R. Falck, Dhurke Kashinath, Narender Puli, Rachid Baati, Steve Tisserand
Rok vydání:	2010
Předmět:	Addition reaction chemistry.chemical_element General Medicine Medicinal chemistry Chloride chemistry.chemical_compound Chromium chemistry Nucleophile Electrophile Propargyl otorhinolaryngologic diseases medicine Triethylamine Carbenoid medicine.drug
Zdroj:	ChemInform. 41
ISSN:	1522-2667 0931-7597
DOI:	10.1002/chin.201033062
Popis:	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.
Databáze:	OpenAIRE
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