Stereogenic propargylic centers via base-mediated terminal allne isomerization

John D. Spence, Justin K. Wyatt, Daniel M. Bender, David K. Moss, Michael H. Nantz

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14 Scopus citations


A study of alkali metal amide-mediated isomerizations of terminal allenes is described. The isomerizations of substituted ethenylidenecyclohexanes to form diastereomeric mixtures of terminal alkynes have been conducted to determine factors which may influence the stereochemistry at the newly formed propargylic centers. An initial base screen revealed that potassium N-methylbutylamide (KMBA) exhibits the highest level of equatorial to axial alkyne diastereoselectivity. With the severely hindered terminal allene 26, the use of potassium 3-aminopropylamide is required to effect isomerization. A general synthesis of deuterated terminal allenes has also been achieved, and a mechanistic study using d2-allenes 18a,b has revealed the involvement of a propargylic anion in the course of the KMBA-mediated isomerizations.

Original languageEnglish (US)
Pages (from-to)4014-4021
Number of pages8
JournalJournal of Organic Chemistry
Issue number12
StatePublished - Jun 14 1996

ASJC Scopus subject areas

  • Organic Chemistry


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