Rapid and easy access to (E)-1,3-enynes, 1,3-diynes and allenes starting from propargylic acetals, exploiting the different reactivity of lithium and mixed lithium-potassium organometallic reagents

European Journal of Organic Chemistry

Volumn , Issue 35, 2007, Pages 5867-5874

  Blangetti, Marco ^a   Deagostino, Annamaria ^a   Rosso, Helèna ^a   Prandi, Cristina ^a   Zavattaro, Chiara ^a   Venturello, Paolo ^a  

^a UNIVERSITY OF TURIN   (Italy)

Author keywords

Acetals; Diynes; Enynes; Metalation; Superbases

Indexed keywords

EID: 37349120022     PISSN: 1434193X     EISSN: 10990690     Source Type: Journal    
DOI: 10.1002/ejoc.200700520     Document Type: Article

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44. Cumulene rearrangement to enyne in basic medium has already been reported, see: W. Pitsch, B. König, Synth. Commun. 2001, 31, 3135-3139.
45. 2 newly formed in the reaction medium could trap the metallated enol ether intermediate so that no further conjugate elimination is possible. The additional equivalent of LDA therefore metallates the acetylenic position to give D.
46. 3SiCl as an electrophile, 1-ethoxybut-1-en-3-yn-2-yltrimethylsilane was captured when the reaction temperature was kept below -78°C, even after the addition of the electrophile. In our opinion, these results corroborate the hypothesis that the base selectively metallates the β-vinyl site of the newly formed enyne. The formation of the conjugated system of diyne 4 can be therefore considered the driving force that leads to the observed selectivity. Notwithstanding this, we cannot exclude that 6 could be an intermediate which, in the presence of the base, undergoes a Fritch-Buttenberg-Wiechell rearrangement. We thank one of the referees for this suggestion.